WO2006063501A1 - Supported non-metallocene olefin polymerization catalyst, and preparation and use thereof - Google Patents

Supported non-metallocene olefin polymerization catalyst, and preparation and use thereof Download PDF

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Publication number
WO2006063501A1
WO2006063501A1 PCT/CN2005/001737 CN2005001737W WO2006063501A1 WO 2006063501 A1 WO2006063501 A1 WO 2006063501A1 CN 2005001737 W CN2005001737 W CN 2005001737W WO 2006063501 A1 WO2006063501 A1 WO 2006063501A1
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Prior art keywords
catalyst
group
polymerization
olefin polymerization
solvent
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PCT/CN2005/001737
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French (fr)
Chinese (zh)
Inventor
Houliang Dai
Houping You
Chuanfeng Li
Xiaoli Yao
Lijin Zhou
Xiaoqiang Li
Yaming Wang
Zhonglin Ma
Jiye Bai
Original Assignee
Yangzi Petrochemical Company Co., Ltd.
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Priority claimed from CN 200410066070 external-priority patent/CN1789291A/en
Priority claimed from CN 200410066069 external-priority patent/CN1789292A/en
Priority claimed from CNB2004100660686A external-priority patent/CN100362024C/en
Application filed by Yangzi Petrochemical Company Co., Ltd. filed Critical Yangzi Petrochemical Company Co., Ltd.
Priority to US11/793,046 priority Critical patent/US7875568B2/en
Priority to EP05801846.6A priority patent/EP1829897B1/en
Priority to JP2007545817A priority patent/JP5346469B2/en
Publication of WO2006063501A1 publication Critical patent/WO2006063501A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the present invention relates to the field of heterogeneous catalyst technology, and in particular to a method for preparing a supported non-metallocene olefin polymerization catalyst, which is a method for supporting a non-metallocene olefin polymerization catalyst on a support, and by the method A supported non-metallocene olefin polymerization catalyst prepared.
  • the invention further relates to the use of the supported non-metallocene olefin polymerization catalyst for the polymerization of olefins and the copolymerization of two or more different olefins.
  • the present invention relates to the use of the supported non-metallocene olefin polymerization catalyst in slurry ethylene polymerization, in other words, low pressure slurry ethylene treatment using the supported non-metallocene olefin polymerization catalyst of the present invention. polymerization. Background technique
  • Homogeneous transition metal catalysts are known to have high catalytic activity in olefin polymerization, such as unsupported Ziegler-Natta catalysts, metallocene olefin polymerization catalysts, defined geometry olefin polymerization catalysts or non-metallocene olefin polymerizations. catalyst.
  • the coordination atom of the non-metallocene olefin polymerization catalyst is oxygen, nitrogen, sulfur and carbon, and does not contain a cyclopentadienyl group.
  • the formed polymer will produce the phenomenon of sticking the kettle and winding the stirring paddle, which has a great influence on the normal operation of the reactor and the heat exchange of the materials in the reactor, which is not conducive to industrial continuous production.
  • a large amount of cocatalyst fluorenyl aluminoxane is required in the homogeneous catalytic system, which increases the production cost of polyolefin, and also has an adverse effect on product performance due to the introduction of a large amount of cocatalyst, and some even need to be in the latter order.
  • the removal of aluminum introduced during the polymerization during processing further increases the cost of the process.
  • An olefin polymerization and copolymerization catalyst or catalytic system prepared by the patent W003/010207 has a wide range of olefin polymerization and copolymerization properties, and is suitable for various forms of polymerization processes, but requires a higher amount of cocatalyst in the polymerization of olefins. A suitable olefin polymerization activity is obtained, and there is a sticking phenomenon in the polymerization process. According to the experience of industrial application of metallocene olefin polymerization catalysts (Chem Rev, 2000, 100: 1347; Chem Rev, 2000, 100: 1377), loading of a homogeneous non-metallocene olefin polymerization catalyst is necessary.
  • the main purpose of catalyst loading is to improve the polymerization properties of the catalyst and the granulation morphology of the polymer. It is characterized by appropriately reducing the initial activity of the catalyst to a certain extent, thereby reducing or even avoiding agglomeration or agglomeration in the polymerization process; the catalyst can improve the morphology of the polymer and increase the apparent density of the polymer after being supported. It can satisfy more polymerization processes, such as gas phase polymerization or slurry polymerization, and the loading process can greatly reduce catalyst preparation and olefin polymerization cost, improve polymerization performance, and prolong the polymerization activity life of the catalyst.
  • EP 0206794 uses MA0 to modify the oxide support and subsequently the metallocene, which objectively limits the ability of the support material to control the particle size of the polymer.
  • EP 685494 The action of methylaluminoxane on hydrophilic oxides, the use of polyfunctional organic crosslinkers and the subsequent use of activated MAO/metallocene complexes, has the potential to reduce the bulk density of the polymerized product, which is detrimental to industrial use.
  • Patent CN 1352654 selects a single-center olefin polymerization catalyst which is treated with an organoaluminum, a silicone, an organomagnesium and an organoboron compound, and then carries a hetero atom ligand, and the resulting supported catalyst has high activity and long shelf life.
  • EP 295 312 describes contacting an aluminoxane solution with a solvent which does not dissolve the aluminoxane in the presence of an organic or inorganic particulate carrier, resulting in precipitation of the aluminoxane on the support.
  • W0 97/26285 describes a method for preparing a supported metallocene catalyst at high pressure with a long production cycle and low loading efficiency.
  • CN 1307065 is supported by a metal aluminoxane after the carrier is treated with an alkyl aluminoxane, and the loading process is not economical.
  • CN 1162601 continues to treat the support treated with the aluminoxane or the alkylaluminum compound using a bifunctional crosslinking agent.
  • Patent CN 1174849 after treating the dehydroxylated silica with MA0 in a toluene medium, and then supporting the metallocene catalyst, the polymerization activity data of the supported catalyst is not given herein.
  • Patent CN1120550 proposes a catalyst loading method, which mainly comprises a hydrophilic, macroporous, finely divided inorganic carrier, which is first thermally activated and then reacted with an aluminoxane, and then reacted with a polyfunctional organic crosslinking agent, and finally The reaction product of the metallocene and the activator is mixed to produce a supported metallocene catalyst, but the amount of aluminoxane is higher during the loading process.
  • CN 1053673 The use of microwaves to contact a catalyst and a cocatalyst supported on a support material in a suspension to produce a supported catalyst of stable structure, but this method requires microwave The device is not easy to operate.
  • Patent WO 96/00243 describes a process for the preparation of a supported catalyst composition comprising mixing a bridged bis-indenyl metallocene and an aluminoxane in a solvent to form a solution, and then combining the solution with a porous support, wherein The total volume of the solution is lower than the volume of the solution when the slurry is formed.
  • Catalysts based on anhydrous magnesium chloride show higher catalytic activity during the polymerization of olefins, but such catalysts are very brittle and are easily broken in the polymerization reactor, resulting in poor polymer morphology.
  • Silica-supported catalysts have good flow properties and can be used in gas phase fluidized bed polymerization, but silica supported metallocene and non-catalysts exhibit lower catalytic activity. Therefore, if magnesium chloride and silica are well combined, it is possible to prepare a catalyst having high catalytic activity, controlled particle size and good wear resistance.
  • EP 0878484 4 is a catalyst prepared by using a MgCl 2 /S i0 2 dual support supported zirconium metallocene with a low magnesium chloride content (less than 3%) for homopolymerization or copolymerization of ethylene, and has good catalytic activity.
  • Patent CN 1364817 discloses a preparation method and a polymerization application of a magnesium chloride/silica supported ⁇ -diketone semi-titanium metal catalyst having an ethylene polymerization activity of 7.42 x 10 sg of polyethylene per mole of titanium. There is no specific data on the granulation properties of the polymer.
  • Patent EP 260130 proposes to support a supported metallocene or non-auxiliary transition metal catalyst on a methylaluminoxane-treated silica support, where the non-roamed transition metal merely refers to ZrCl 4 , TiCl 4 or V0C1 3 , the patent Most preferably, the surface of the support is a mixture of organomagnesium or a ruthenium compound and an aluminum alkyl, but this process is complicated and requires many preparation steps.
  • Patent CN1539856A proposes to support a non-metallocene catalyst on a composite support formed of silica and magnesium chloride, and the supported non-metallocene catalyst and methylaluminoxane thus obtained are used in a polymerization catalyst system for olefin polymerization.
  • Patents W003/ 047752A1 and W003/047751A1 provide a method for loading a composite catalyst (Ziegler-Natta with a metallocene catalyst, or a non-metallocene catalyst and a metallocene catalyst) on silica, the patent claims that titanium or vanadium Chloride or oxychloride It is a non-metallocene catalyst component, and the catalyst thus obtained is a bimetallic catalyst.
  • the activity of the olefin polymerization catalyst is a primary condition for its application.
  • the non-metallocene catalyst is supported by an inert carrier, the catalytic olefin polymerization activity is more or less reduced, and some even reduce the activity by more than an order of magnitude, resulting in an uneconomical application of the supported catalyst.
  • the ash content of the obtained polymer is increased, and an additional deliming process is required in the production, which leads to an increase in cost and complexity of the production apparatus, and limits its further application in the catalytic production of polyolefin.
  • the polymerization system based on different catalysts mainly includes the following: High pressure process, polymerization pressure greater than 50 MPa, using a stirred tank or a tubular reactor.
  • Exxon was first developed and produced Exact® with Exxpol® single-site catalyst at the Baton Rouge high pressure polymerization plant, with properties ranging from elastomers to low density polyethylene thermoplastics.
  • the high-pressure process has high requirements on equipment and the investment in fixed assets is huge.
  • the solution method is more suitable for homogeneous single-site catalysts.
  • the fluidized bed of UCC and BP, and the stirred bed reactor of Mariac are the most typical.
  • the slurry method has a wide range of applications. The most typical in the industry is the continuous loop reaction process of Phi ll ips and Solvay, the stirred tank reactor of Mariac, the Nissan, and the three-cylinder fe-mix reactor of Mitsui.
  • the slurry method has no agitation viscosity problem, the reaction medium is uniform, and the reaction heat is easily eliminated; the polymerization yield is high, the polymer having a very high weight average molecular weight can be produced, and the energy saving and investment cost and production cost of the recovered polymer are low.
  • W09729138 discloses that in a fluidized bed reactor, it is possible to increase the ethylene partial pressure by lowering the partial pressure of ethylene and using a non-polymerization temperature. The best result is that ethylene has a partial pressure of 60 to 120 Ps i and a reaction temperature of 90 to 120. The patent found that this ethylene homopolymerization process is independent of the type of supported metallocene.
  • the polymerization process of the catalyst it is necessary to consider the adaptability of the polymerization process to the catalyst, the investment cost, and the complexity and cost of the operation of the device, and also refer to the performance adjustment and control of the polymerization product by referring to the polymerization process, and changing the polymerization conditions and products. Between performance Correspondence relationship.
  • the high pressure process and the solution process are suitable for unsupported metallocene catalysts or non-metallocene catalysts, while the gas phase process and the slurry process are most suitable for supported metallocene catalysts or non-metallocene catalysts.
  • the present invention relates to a method of loading a non-metallocene olefin polymerization catalyst on a support.
  • the supported method of the support-supported non-metallocene olefin polymerization catalyst of the present invention comprises the following steps:
  • the carrier is allowed to react with a chemical activator to obtain a modified carrier
  • the magnesium compound is dissolved in a tetrahydrofuran-alcohol mixed solvent to form a solution, and the modified carrier is added to the solution to carry out a reaction, followed by filtration washing, drying and drying to obtain a composite carrier;
  • the non-metallocene olefin polymerization catalyst is dissolved in a solvent, then reacted with the composite support, followed by washing, filtration, drying and drying to obtain a supported non-metallocene terpene hydrocarbon polymerization catalyst.
  • An optimization of the above method is to add one or both of the following steps: the carrier is subjected to a superheat activation treatment before the action with the chemical activating agent; the composite carrier is reacted with the non-metallocene olefin polymerization catalyst Previously, a modified composite support is prepared by reacting with a chemical treatment agent, and then the modified composite support is reacted with the non-metallocene olefin polymerization catalyst to prepare the supported non-metallocene olefin polymerization catalyst.
  • the non-metallocene olefin polymerization catalyst according to the present invention is a complex having the following structure: -IVIXn among them:
  • n 1 or ⁇
  • d 0 or 1
  • n stands for 1, 2, 3 or 4;
  • M represents a transition metal atom
  • X is selected from a halogen atom, a hydrogen atom, and C 3 . Hydrocarbyl group and C 3 . Substituted hydrocarbyl group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, ruthenium-containing group, or tin-containing group a group, several ligands X may be the same or different, and may also be bonded or looped to each other;
  • the absolute value of the total negative charge of all ligands in the structural formula should be the same as the absolute value of the positive charge of the metal M in the structural formula, and all ligands include ligand X and multidentate ligands,
  • polydentate ligand refers to R in the structural formula
  • A represents an oxygen atom, a sulfur atom, a selenium atom, R 21 N or R 21 P;
  • Table B contains a nitrogen group, a phosphorus containing group or Ci - C 3 . Hydrocarbons;
  • D represents an oxygen atom, a sulfur atom, a selenium atom, an ( ⁇ - C 3 hydrocarbon group is a nitrogen-containing group, containing ( ⁇ - a nitrogen-containing hydrocarbon group or a C 3 containing -.
  • an ( ⁇ - C 3 hydrocarbon group is a nitrogen-containing group, containing ( ⁇ - a nitrogen-containing hydrocarbon group or a C 3 containing -.
  • E represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordinating atoms;
  • the II 1 , R 2 , R 3 , R 21 groups may be the same or different from each other, wherein adjacent groups such as RR 2 , R 3 moieties may be bonded or ringed to each other;
  • the hydrocarbon group means C 3 .
  • the catalyst is preferably a non-metallocene catalyst having the following structure:
  • the above non-metallocene olefin polymerization catalyst is further a compound having the following structure:
  • n 1, 2 or 3
  • d 0 or 1
  • M represents a transition metal atom, especially titanium, zirconium, hafnium, chromium, iron, cobalt, nickel or palladium;
  • N represents 1, 2, 3 or 4;
  • X is a halogen atom, a hydrogen atom, a hydrocarbon group of CI - C30, a substituted hydrocarbon group of C1 - C30, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus group, a silicon-containing group, a hydrazine-containing group, or a group containing a group, wherein several ligands X in the structural formula may be the same or different, and may also be bonded or ring-bonded to each other;
  • the halogen atom herein includes fluorine, chlorine, bromine or iodine;
  • the absolute value of the total negative charge of all ligands in the structural formula shall be the same as the absolute value of the positive charge of the metal M in the structural formula, and all ligands include ligand X and polydentate ligand, wherein
  • Multidentate ligand refers to the structural formula ;
  • A represents an oxygen atom, a sulfur atom, a selenium atom, I, a NR 23 R 24 , an N(0)R 25 R 26 , , a PR 28 R 29 , a P (0) R 3 .
  • R 31 sulfone group, sulfoxide group or a Se(0)R 39 ;
  • B represents a nitrogen-containing group, a phosphorus-containing group or C 3 .
  • Hydrocarbons
  • D represents an oxygen atom, a sulfur atom, a selenium atom, and contains ( ⁇ -( 3 . a hydrocarbon group-containing nitrogen group, a hydrocarbon group containing a group, a sulfone group, a sulfoxide group, -P(0)R 3 °R 31 or a P(0)R 32 (OR 33 ), wherein N, 0, S, Se, P are coordination atom;
  • E represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordinating atoms;
  • F represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a group-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordination atoms;
  • G represents an inert group or an inert functional group, including -C 3 .
  • Hydrocarbyl group, -C 3 Substituted hydrocarbyl or inert functional group;
  • Y, z represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a solid-containing or phosphorus-containing group, N, 0, S, Se, P are coordination atoms;
  • - represents a single key or a silent key
  • ... represents a coordination bond, a covalent bond or an ionic bond
  • One represents a covalent bond or an ionic bond
  • R 20 R 21 R 22 R 23 R 24 R 27 R 28 R 29 R 30 R 31 R 32 R 33 R 34 R 35 R 36 R 38 and R 39 are selected from the group consisting of hydrogen and C 3 .
  • a hydrocarbon group, a halogen atom, a substituted hydrocarbon group of ( ⁇ -0 3 (particularly a halogenated hydrocarbon group such as a CH 2 C1 or a CH 2 CH 2 C1 ) or an inert functional group the above groups may be the same as each other Different, wherein adjacent groups such as R 1 and R 2 , R 3 , R 3 and R 4 , R 6 R 7 , R 8 , R 9 and R 23 and R 24 or R 25 and R 2S may be bonded to each other Or into a ring;
  • R 5 represents a lone pair of electrons on the nitrogen, hydrogen, ( ⁇ -C 3 . a hydrocarbyl group, a substituted hydrocarbyl group of ⁇ -C, an oxygen-containing group, including a hydroxyl group, an alkoxy group - OR 34 , an alkyl group having an ether group , comprising a T-OR 34 , a sulfur-containing group, including -SR 35 , -T-SR 35 , a nitrogen-containing group, including -NR 23 R 24 , -T-NR 23 R 24 , a phosphorus-containing group, including a PR 28 R 29 , - T-PR 2S R 29 , — T— P (0) R 3 °R 31 ; when R 5 is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a group-containing group or In the case of a phosphorus-containing group, 1 (, 0, S, P, Se in R 5 may also participate in the coordination of the metal;
  • T stands for Ci-C 3 . a hydrocarbyl group, a substituted hydrocarbyl group of C 3Q or an inert functional group.
  • the non-metallocene olefin polymerization catalyst may, for example, be exemplified by the following non-metallocene olefin polymerization catalyst:
  • a preferred structure is a non-metallocene olefin polymerization catalyst as shown below
  • non-metallocene olefin polymerization catalysts having the structure shown below:
  • the fact that the element and the metal belong to a certain family means that the family and the group according to the periodic table of the elements correspond to the group or group grouped by the IUPAC system.
  • the porous solid used in the present invention may be any porous solid having a functional group on its surface. It may be: a copolymer of an organic material containing an organic functional group such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and a monomer on which the above polymer is based, polyester, polyamide, polyvinyl chloride , polyacrylate, polydecyl acrylate, polystyrene, or partially crosslinked polymer, and the organic functional group is selected from the group consisting of hydroxyl, primary, secondary, sulfonic, carboxy, amide, N-monosubstituted Amido, sulfonate amine, N-monosubstituted phosphonic acid, sulfhydryl, imido and hydrazide groups.
  • an organic functional group such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and a monomer
  • a styrene polymer Preferably partially crosslinked, having surface hydroxyl functional groups a styrene polymer, preferably also a polystyrene having a carboxyl group on the surface; a solid inorganic oxide selected from the group consisting of ruthenium, osmium, IVA and IVB metal oxides or a halide of these metals, such as silica (also Known as silica gel), alumina, magnesia, titania, zirconia, cerium oxide, magnesium chloride, and mixtures and mixed oxides of these inorganic oxides, the functional groups of which are selected from surface hydroxyl or carboxyl groups; or by gaseous metals An oxidizing material prepared by a high temperature hydrolysis process of an oxide or a silicon compound; or clay, molecular sieve, mica, montmorillonite, bentonite, diatomaceous earth, ZSM-5 or MCM-41.
  • More suitable as the carrier of the present invention is a surface having a hydroxyl group, including silicon dioxide, and a mixed oxide of silicon dioxide and one or more anthracene or lanthanum metal, such as silica-magnesia mixed oxidation.
  • silica-alumina mixed oxide preferably a silica, alumina and a mixed oxide of silicon dioxide and one or more lanthanum and lanthanum metal oxides as a support material, particularly preferably oxidizing Silicon
  • a carrier suitable silica carrier is any commercially available product such as Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davs ion Syloid 245, ES70, ES70X , ES70Y, ES757, Aeros il812, or CS-2133 and MS-3040
  • the silica is dried or calcined for 1 to 24 hours for heat activation before being used in the carrier, preferably under 100-1000, inert atmosphere or reduced pressure.
  • the surface area (determined by the BET method) of the carrier suitable for the present invention is preferably from 10 to 1000 m 2 /g, more preferably from 100 to 600 m 2 /g. 2 ⁇ 2 ⁇ 3 /g ⁇
  • the carrier pore volume (measured by the nitrogen adsorption method) is preferably 0. 1 ⁇ 4cm 3 / g, more preferably 0. 2 ⁇ 2cm 3 / g.
  • the average particle diameter of the carrier is preferably from 1 to 500 ⁇ m, more preferably from 1 to 100 ⁇ m.
  • a solid inorganic oxide or halide carrier having a surface hydroxyl group selected from the group consisting of ruthenium, osmium, group IVA and group IVB metal oxides is preferred, and silica is most preferred. It may be in any form, such as granules, spheres, aggregates or other forms.
  • the hydroxyl group content can be determined by known techniques such as infrared light, nuclear magnetic resonance, titanium tetrachloride, metal alkyl or metal hydride titration techniques.
  • the chemical activator herein may be, for example, a metallization, a metal alkylate, a metal alkoxide or a mixture thereof, specifically, for example, a ruthenium, an IVB or a VB group metal compound, an alkyl compound or a 13 ⁇ 4 generation.
  • the alkyl compound, or a metal alkoxide is preferably a halide of a metal of the FFA, IVB or VB group, an aluminum alkyl or an aluminoxane or the like.
  • the halide of the cerium, IVB or VB group metal for example, aluminum trichloride, aluminum tribromide, aluminum triiodide, titanium tetrachloride, titanium tetrabromide, titanium tetrahydrate, zirconium tetrachloride, Zirconium tetrabromide, zirconium tetraiodide, antimony tetrachloride, antimony tetrabromide, antimony tetraiodide, vanadium chloride, vanadium bromide, Decompose vanadium and so on.
  • bismuth-based aluminum examples include methyl aluminum, ethyl aluminum, propyl aluminum, isobutyl aluminum or butyl aluminum. Preferred are ethyl aluminum and isobutyl aluminum, most preferably ethyl aluminum;
  • halogenated alkyl compound examples include chloromercaptoaluminum, dichloroindenyl aluminum, monochloroethylaluminum, dichloroethylaluminum, monochloropropylaluminum, dichloropropylaluminum, and monochloroisobutylaluminum. , dichloroisobutyl aluminum, monochlorobutyl aluminum, dichlorobutyl aluminum, and the like.
  • the aluminoxane can be linear (I):
  • the R groups may be the same or different and are C1-C8 alkyl groups, and the aluminoxanes include mercaptoaluminoxane, ethylaluminoxane, isobutylaluminum oxide Alkane or butyl aluminoxane, and the like.
  • the R groups are the same and are a methyl group, an ethyl group or an isobutyl group, most preferably a fluorenyl group, and ⁇ is an integer of from 1 to 50, preferably from 10 to 30.
  • the aluminoxane represented by the above structural formula is preferably, for example, mercaptoaluminoxane (MA0), ethylaluminoxane (EA0), isobutylaluminoxane (IBA0) or the like.
  • the aluminoxane is selected, for example, from methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane or modified decyl aluminoxane. .
  • Eudraphanyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane or modified methyl aluminoxane most preferably methyl aluminoxane.
  • the reaction of the chemical activator with the carrier can be carried out by any method as long as the carrier can be brought into contact with the chemical activator to cause it to react.
  • the following methods can be mentioned.
  • Adding the solvent to the carrier, stirring below the boiling point of the solvent, and adding a chemical activator or a chemical activator solution, such as a liquid chemical activator used in hydrazine, can be directly added. If a solid chemical activator is used, it should first Dissolve solid chemical activator This solvent is then added. The method of addition is dripping. The reaction was filtered for 0.5 to 24 hours, and washed with the same solvent for 1 to 8 times and then dried.
  • the solvent described herein is also arbitrary as long as it can dissolve the chemical activator or be miscible with the chemical activator, such as a liquid hydrocarbon selected from C5 to C12, an aromatic compound or a surface hydrocarbon such as pentane.
  • a liquid hydrocarbon selected from C5 to C12, an aromatic compound or a surface hydrocarbon such as pentane.
  • reaction temperature of the chemical activator and the carrier should be lower than the boiling point of the solvent.
  • the reaction temperature can be selected between 20 ⁇ and 65
  • the temperature can be selected at 20 ° C.
  • the reaction temperature varies depending on the solvent, and it cannot be generalized, but it is generally selected to be between 5 and 101 C below the boiling point of the solvent, and the reaction time is not particularly limited, and generally 0.5 to 4 hours can be selected. In the case where the reaction temperature is raised, the reaction time can be appropriately shortened.
  • reaction of the chemical activator with the support can be carried out in the absence of a solvent.
  • the chemical activator must be in a liquid state, but the reaction temperature and reaction time can be appropriately determined according to needs, but the reaction temperature should be at least 5 ⁇ 10" ⁇ below the boiling point of the chemical activator, and the time is 2 ⁇ 24 hours.
  • Chemical activator The more intense the reaction with the carrier, the lower the reaction temperature and the longer the time. For example, when the chemical activator is titanium tetrachloride, the reaction temperature can be between -30 ⁇ and 126 , and the corresponding time is 12 to 2 hours.
  • the mass ratio between the magnesium compound and the modifying carrier is 1: 0.1-40, preferably 1: 1-10.
  • the reaction conditions are 0 to 130 Torr, and the reaction time is 0.1 to 8 hours.
  • the magnesium compound is selected from the group consisting of magnesium, alkoxymagnesium halide, magnesium alkoxide, or a mixture thereof.
  • the tetrahydrofuran-alcohol mixed solvent is selected from the group consisting of tetrahydrofuran-fatty alcohol, tetrahydrofuran-cycloalcohol or tetrahydrofuran-aromatic alcohol or tetrahydrofuran-ethanol.
  • the magnesium compound is preferably a magnesium halide, most preferably magnesium chloride.
  • the solvent used in the catalyst loading step may be a solvent commonly used in catalyst loading methods in the art, and may be selected from mineral oils and different liquid hydrocarbons.
  • Typical solvents are hydrocarbon solvents of 5 to 12 carbon atoms, or hydrocarbon solvents substituted by chlorine atoms, such as dichloromethane, or ether-based solvents such as diethyl ether or tetrahydrofuran, and acetone or ethyl acetate. Can also be used.
  • the solvent is preferably an aromatic solvent such as toluene and dinonylbenzene; or an aliphatic solvent of 6 to 10 carbon atoms such as hexane, heptane, octane, decane, decane and isomers thereof; A cycloaliphatic solvent to 12 carbon atoms, such as hexane; or a mixture thereof. Most preferred is tetrahydrofuran, toluene or hexane.
  • the concentration of the non-metallocene olefin polymerization catalyst in the solvent may be a concentration commonly used in the catalyst loading method in the art, and is generally 0.1 to 1 gram of catalyst per liter of solvent.
  • the non-metallocene olefin polymerization catalyst is dissolved in a solvent, and then contacted with the composite carrier, by solution impregnation, or an equal volume impregnation method, or by solution impregnation, filtration drying, and then an equal volume impregnation method, thereby completing the non-macro The loading process of the metal catalyst on the support.
  • the surface of the metal oxide generally has an acidic surface hydroxyl group which can be reacted with the catalyst to inactivate it.
  • the support Prior to use, the support is subjected to a dehydroxylation process which may be activated by calcination under vacuum or an inert atmosphere.
  • the activation of the carrier is carried out at 100-100 (TC, inert atmosphere or under reduced pressure for 1 to 24 hours.
  • the inert atmosphere referred to herein means that the gas contains only a trace amount and does not contain a component which can react with the carrier.
  • the calcination conditions are preferably maintained in an atmosphere of 500 to 800 Torr, ⁇ or Ar for 2 to 12 hours, most preferably 4 to 8 hours. It is known to those skilled in the art that the thermally activated carrier needs to be stored under an inert atmosphere.
  • the purpose of superheat activation of the silica support is to provide a highly active group on the surface of the support, as reported (J Am Chem Soc, 1996, 118: 401), when the drying temperature is 200 ° C ⁇ At 500 Torr, the easily removable hydroxyl group is reversibly removed, resulting in a low reactivity siloxane group, but at a drying temperature of more than 600 Torr, the hydroxyl group is forcibly removed and converted into water. A siloxane group having a high cyclic stress and a high reactivity is produced. Chemical activators can also be used to convert functional groups on the surface of the support to other unreacted siloxane groups.
  • the composite support of the present invention can be directly catalyzed by polymerization with non-metallocene olefins.
  • the solution is contacted to obtain the highly active supported non-metallocene olefin polymerization catalyst of the present invention after the loading.
  • the composite support is preferably subjected to further treatment to obtain a modified composite support. The cost of this processing step is negligible compared to the additional activity obtained thereby.
  • the composite carrier is contacted with a chemical treatment agent, and the contact process is carried out by a solution impregnation method in which the composite carrier is immersed in a chemical treatment solution and treated under stirring.
  • the chemical treatment agent is selected from the group consisting of aluminide, alkyl aluminum, borane, IVA, IVB or VB metal halides, alkyl compounds, alkoxy compounds or! One or more of the 3 ⁇ 4 alkyl compounds.
  • the halide of the IVA, IVB or VB group metal may, for example, be silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or zirconium tetrachloride.
  • Examples of the aluminum alkyl group include methyl aluminum, ethyl aluminum, propyl aluminum, isobutyl aluminum or butyl aluminum. Preferred are ethyl aluminum and isobutyl aluminum, most preferably ethyl aluminum;
  • halogenated alkyl compound examples include monochloroindolyl aluminum, dichloromethylaluminum, ethylachloroethylaluminum, dichloroethylaluminum, monochloropropylaluminum, dichloropropylaluminum, and monochloroisobutylaluminum.
  • the aluminoxane may be a linear type (I) and/or a cyclic aluminoxane aluminoxane such as decyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, isobutyl aluminum.
  • methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or modified methylaluminoxane is preferred, and mercaptoaluminoxane is most preferred.
  • the chemical treatment agent may be selected from various combinations of the above, a combination of two, such as silicon tetrachloride and ethyl aluminum, silicon tetrachloride and methyl aluminoxane, silicon tetrabromide and ethyl aluminum, silicon tetrabromide and Methylaluminoxane, titanium tetrachloride and ethylaluminum, titanium tetrachloride and decyl aluminoxane, silicon tetrachloride and ethylaluminum chloride, silicon tetrachloride and ethylaluminum dichloride, tetrachloro Titanium and ethylaluminum chloride, titanium tetrachloride and ethylaluminum dichloride, ethylaluminum and mercaptoaluminoxane, monochloroethylaluminum and mercaptoaluminox
  • Combination of three such as titanium tetrachloride, ethyl aluminum and bismuth aluminum Oxyalkane, silicon tetrachloride, ethyl aluminum and mercaptoaluminoxane, and the like.
  • Various combinations of chemical treatment agents are preferably a combination of two, such as silicon tetrachloride and ethyl aluminum, silicon tetrachloride and methyl aluminoxane, titanium tetrachloride and ethyl aluminum, titanium tetrachloride and bismuth aluminum.
  • the oxane, ethylaluminum and decyl aluminoxane are most preferably titanium tetrachloride and ethylaluminum, titanium tetrachloride and decyl aluminoxane.
  • the reaction of the chemical treatment agent with the composite carrier can be carried out by any method as long as the composite carrier can be brought into contact with the chemical treatment agent to cause it to react.
  • the following methods can be mentioned.
  • the solvent described herein is also arbitrary as long as it can dissolve the chemical treatment agent or is miscible with the chemical treatment agent, such as a liquid hydrocarbon selected from C5 to C12, an aromatic compound or a hydrocarbon-forming compound such as pentane or Alkane, heptane, octane, decane, decane, undecane, dodecane, cyclohexane, toluene, ethylbenzene, xylene, chloropentane, chlorohexan, chloroheptane, Chlorooctane, chlorohydrazine, chlorodecane, chlorodecane, chlorododecane, chlorocyclohexane, chlorophenylbenzene, chloroethylbenzene, chlorinated diphenylbenzene, etc. Pentane, hexane, decane, cyclohexane, toluene are preferred, and
  • reaction temperature varies depending on the solvent. Generally, the maximum temperature should be selected from the boiling point of the solvent below 5 to 10 Torr.
  • the reaction time is not particularly limited, but the reaction time can be appropriately shortened in the case of increasing the reaction temperature.
  • the ratio of the composite carrier to the chemical treatment agent in contact is 1 gram: 1 to 100 Torr, and the preferred ratio is 1 gram: 2 - 25 Torr.
  • the composite carrier is subjected to a treatment with a chemical treatment agent, washed, washed, dried and dried to obtain a modified composite carrier.
  • the ratio of the shield of the modified composite support to the non-metallocene olefin polymerization catalyst is 1:0.01 - 0. 50, and the preferred mass ratio is 1:0.05 - 0 30.
  • Washing, filtering, drying and draining of the composite carrier or modified composite carrier can be carried out by methods well known in the art, such as rinsing, i.e., in a closed or active atmosphere, in a non-passible manner.
  • the solid is rinsed but can be passed through the solvent core of the funnel, and the solvent is repeatedly washed to achieve the purpose of washing and filtering; or the rinsing is carried out, that is, the upper liquid is removed after standing, and then the solvent is added, so that the process is repeated to achieve the washing and filtering.
  • the most common method is to wash the filtered system into the sand core funnel, remove the solvent by suction filtration, then add the solvent, and then suction filtration to achieve the purpose of washing and filtering. method.
  • the washing and filtering process is preferably repeated 2 to 4 times.
  • the solid is dried under reduced pressure at a temperature of about 0 to 120 ° C until a fluid catalyst carrier powder is obtained.
  • the length of this drying process depends on the temperature used and is related to the capacity of the vacuum system and the containment of the system.
  • the supported non-metallocene hydrocarbon polymerization catalyst can be produced by the supported method of the support-supported non-metallocene olefin polymerization catalyst of the present invention, which is an organic whole composed of a non-metallocene olefin polymerization catalyst and a carrier, and a cocatalyst When used together to form a catalytic system, it can be used to catalyze the homopolymerization or copolymerization of olefins. Accordingly, in one embodiment, the present invention relates to a supported non-metallocene olefin polymerization catalyst produced by the supported method of the support-supported non-metallocene olefin polymerization catalyst of the present invention.
  • Another object of the present invention is to carry out catalytic polymerization of olefins or to carry out copolymerization between different terpene hydrocarbons using the supported non-metallocene catalyst of the present invention.
  • the novel method of the present invention overcomes the disadvantages of the conventional multi-active unsupported Ziegler-Natta catalyst in that the polymerization product has poor regularity and can only produce low-end products, and adopts the single-active load type of the present invention.
  • the non-metallocene olefin polymerization catalyst is used for the polymerization or copolymerization of an olefin, a polymerization product having a better degree of regularity can be obtained, thereby meeting the needs of high-end product production.
  • the supported non-metallocene olefin polymerization catalyst of the present invention and a cocatalyst to constitute a catalytic system;
  • the polymerization monomer and/or the copolymerization monomer are introduced into the polymerization reactor under polymerization conditions to carry out olefin polymerization and/or copolymerization.
  • the supported non-metallocene olefin polymerization catalyst of the present invention is used as a main catalyst, and can be used for catalyzing the polymerization and copolymerization of olefins under the action of a cocatalyst.
  • the olefin referred to herein is selected from a C2-C10 olefin, a diolefin or a cyclic olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1- Octene, 1-decene, 1-undecene, 1-dodecene, 1-cyclopentene, norbornene, norbornadiene, or styrene, 1, 4-butadiene, 2, 5 - pentadiene, 1,6-hexadiene, 1,7-octadiene, or a functional group-containing organic monomer such as vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate.
  • a functional group-containing organic monomer such as vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate.
  • the polymerization referred to in the present invention means a homopolymerization of a single double bond-containing olefin, a diolefin, a cyclic hydrocarbon or a functional group-containing organic monomer, and the copolymerization means two , or a polymerization process carried out between two or more olefins, diolefins, cyclic olefins or functional organic groups containing a double bond.
  • the polymerizable monomer is preferably ethylene, and the comonomer copolymerized with ethylene is preferably decene, 1-butene or 1-hexene.
  • a cocatalyst in the catalytic system of the present invention is selected from the group consisting of aluminum alkyls, aluminoxanes, Lewis acids, borofluorocarbons, alkyl boron or alkyl boron ammonium salts.
  • the aluminoxane may be the aluminoxane of the above linear type (I) and/or cyclic aluminoxane (?).
  • the aluminum alkyl or alkyl boron is a compound having the following formula (ffl):
  • N is aluminum or boron
  • R is the same as defined in structures (I) and ( ⁇ ), and each of the three R groups may be the same or different.
  • Specific examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimercapto aluminum chloride, triisopropyl aluminum, tri-sec-butyl aluminum, and three Cyclopentyl aluminum, triamyl aluminum, triisoamyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triamyl aluminum, tri-p-phenylene aluminum, dimethyl Aluminium decyl alcohol, dimethyl aluminum ethoxide, trimethyl ammonium tetraphenyl aluminum, trimethyl boryl, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron or trimethyl Ammonium tetraphenylboron; and
  • L is a neutral or positive ionic Lewis acid
  • H is a hydrogen atom
  • N is aluminum or boron.
  • Each E may be the same or different and is an aryl group having 6 to 12 carbon atoms in which one or more hydrogens are substituted by a phenol atom, an alkoxy group or a phenoxy group.
  • trimethylammonium tetraphenylboron trimethylammonium tetra(p-nonylphenyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, trimethylphosphinetetraphenylboron, Trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, triammonium ammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o-, p-diphenylphenyl)aluminum, three Butyl ammonium tetrakis(p-trifluoromethylphenyl)aluminum, trimethylammonium tetrakis(p-trifluoromethylphenyl)aluminum, tributylammonium tetrakis(pentaphenoxyphenyl)
  • the cocatalyst used in the olefin polymerization and copolymerization process of the invention is preferably an aluminoxane, most preferably methylaluminoxane.
  • the supported non-metallocene olefin polymerization catalyst of the present invention may be subjected to various methods for catalyzing the polymerization of olefins and copolymerization. Specific examples of such a method include a slurry method, an emulsion method, a solution method, a bulk method, and a gas phase method.
  • the supported non-metallocene olefin polymerization catalyst of the present invention is particularly suitable for use in gas phase processes and slurry processes, and is most suitable for slurry processes.
  • the solvent for polymerization used in the polymerization or copolymerization of the olefin of the present invention may be a solvent commonly used in the field for the polymerization or copolymerization of such an olefin, and may be a mineral oil and a different liquid hydrocarbon.
  • Typical solvents are hydrocarbon solvents of 5 to 12 carbon atoms, or hydrocarbon solvents substituted with chlorine atoms, such as dichloromethane, or ether-based solvents such as diethyl ether or tetrahydrofuran, and acetone or ethyl acetate. use.
  • aromatic solvents such as toluene and diphenylbenzene; or aliphatic solvents of 6 to 10 carbon atoms such as hexane, heptane, octane, decane, decane and their isomers; A cycloaliphatic solvent of 12 carbon atoms, such as hexane; or a mixture thereof.
  • hexane is used as the solvent for the polymerization reaction of the present invention.
  • the manner in which the supported non-metallocene catalyst of the present invention and the cocatalyst are introduced into the polymerization vessel is a critical technical parameter.
  • the introduction method may be that a solvent for polymerization is added to the supported catalyst of the present invention to form a certain concentration of the catalyst suspension, and then a cocatalyst is added to form a catalytic system, and then added to the polymerization reaction vessel, and the catalyst may be suspended.
  • the liquid and the co-catalyst are respectively added to the polymerization reaction tank, and the separately added manner may be that the suspension of the catalyst is first added to the polymerization reaction vessel, and then the co-catalyst is added to the polymerization reaction vessel; or The cocatalyst is added to the polymerization vessel, and then the catalyst suspension is added to the polymerization vessel. Medium; or the catalyst suspension and cocatalyst are simultaneously added to the polymerization vessel through different feed ports.
  • the preferred feeding method of the present invention is to first add a solvent for polymerization to the negative catalyst. A certain concentration of the catalyst suspension is formed, and then a cocatalyst is added to form a catalytic system, which is then added to the polymerization vessel. 0001 - The concentration of the supported catalyst and the concentration of the cocatalyst in the catalyst system is not required to be clarified in the present invention, but the preferred concentration range is 0.
  • the solvent for the polymerization is preferably used in an amount of from 0.01 to 1 gram of the supported catalyst per liter of the solvent for the polymerization and from 0.001 to 100 g of the cocatalyst per liter of the solvent for the polymerization.
  • the pressure of the polymerization is in the field of the conventional pressure in the field, generally between 0.1 to 1 OMPa. Preferably, it is 0.1 to 4 MPa, and most preferably 1 to 3 MPa.
  • Higher polymerization pressure can accelerate the rate of olefin polymerization/copolymerization of supported non-metallocene catalysts, resulting in high yield of polymer, but may result in poor polymer morphology, excellent particle morphology, and freedom after drying. Flowing polymer particles increase the difficulty and cost of subsequent processing. At the same time, lower polymerization pressures can cause many problems, most importantly, activity problems, which can lead to uneconomical polymerization processes.
  • the polymerization temperature conditions are conventional conditions in the art, and are generally -40 ⁇ to 200 ⁇ . At lower polymerization temperatures, the polymerization activity obtained is very limited, which may lead to uneconomical polymerization. Excessive polymerization temperature may result in poor polymer morphology, excellent particle morphology, and dryness. The free-flowing polymer particles increase the difficulty and cost of subsequent processing.
  • the present invention is preferably 10'C to 100, most preferably 40"C to 90".
  • the form in which the comonomer is introduced into the polymerization vessel may be intermittent or continuous.
  • the amount of the comonomer introduced may be from 0.01 to 50% (relative to the total amount of the polymerized product), depending on the need for the copolymerized product after polymerization.
  • agitating paddles such as an anchor paddle, a propeller paddle, an open paddle or a screw paddle are used. Both can be used as the agitating paddle of the present invention to promote dispersion of the polymer material, as well as transfer of heat and mass.
  • a propulsion paddle is preferred.
  • the agitation rate can be 12,000 rpm, preferably 100 to 600 rpm.
  • the olefin polymerization and copolymerization process of the present invention can be carried out in the presence of hydrogen or in the absence of hydrogen. If necessary, hydrogen may be added as a polymer molecular weight regulator, and the partial pressure may be from 0.01% to 99% of the polymerization pressure, and preferably the partial pressure of hydrogen is from 0.01% to 50% of the polymerization pressure.
  • the supported non-metallocene olefin polymerization catalyst of the present invention is particularly suitable for the slurry method.
  • the cocatalyst used in the ethylene slurry polymerization process of the present invention is the same as that previously described for the catalytic polymerization or copolymerization of olefins, and in particular, aluminoxane or alkylaluminum, or a mixture of the two, such as methylaluminoxane, may be used.
  • aluminoxane or alkylaluminum or a mixture of the two, such as methylaluminoxane
  • MA0 Ethyl Aluminoxane
  • IBA0 Isobutyl Aluminoxane
  • TMA Trimethyl Aluminum
  • TAA Triethyl Aluminum
  • TIBA Triisobutyl Aluminum
  • MAO- TEA MAO-TMA
  • MAO-TMA MAO-TMA, etc.
  • the polymerization temperature used in the ethylene slurry polymerization method of the present invention is a conventional temperature in the art, and is generally 10 to 100 Torr, preferably 10 to 95"C, more preferably 30 to 95 ° C, and the polymerization pressure is 0.1 to 3. OMPa, preferably. 0.1 ⁇ 2.0MPa.
  • the ethylene slurry polymerization of the present invention comprises: ethylene homopolymerization, copolymerization of ethylene with C3-C12 olefin, or homopolymerization of ethylene in the presence of hydrogen, copolymerization of ethylene with C3-C12 olefin;
  • C3-C12 may be propylene, butyl Alkene-1, pentene-1, hexene-1, 4-methyl-pentene-1, heptene-1, octene-1, or norbornene.
  • propylene, butene-1, hexene-1, octene-1 and norbornene are preferred, and propylene, butene-1 and hexene-1 are most preferred.
  • hydrogen is generally used as a chain transfer agent in the ethylene slurry polymerization process of the present invention.
  • the amount of hydrogen used may be 0.01 to 0.99 (volume ratio) of the total gas amount, preferably 0.01 to 0.50 (volume ratio).
  • the solvent used in the ethylene slurry polymerization method of the present invention is a hydrocarbon solvent of 5 to 12 carbon atoms, or a hydrocarbon solvent substituted by a chlorine atom, preferably an aromatic solvent of 6 to 12 carbon atoms; or 6 An aliphatic solvent of up to 10 carbon atoms; a cycloaliphatic solvent of 0 to 12 carbon atoms, or a mixture thereof.
  • the polymer bulk density was determined by reference to GB 1636-79.
  • the chemical activator is titanium tetrachloride; the activated carrier is reacted with titanium tetrachloride, filtered, washed and dried to obtain a modified carrier.
  • the mass ratio of titanium tetrachloride to silicon dioxide is 1:40;
  • the magnesium chloride is dissolved in tetrahydrofuran-ethanol'; a solution is formed in the system, and the modified carrier is added to the solution, and fully reacted under a stirring condition of 0 to 60 to form a transparent system.
  • the time is from 1 to 48 hours, preferably from 4 to 24 hours.
  • the composite carrier is prepared by washing, drying and drying.
  • the water content of magnesium chloride should be less than 1% of the shield volume, and the average particle size is 1 ⁇ ⁇ , Youyi 20 ⁇ 40 ⁇ ; the specific surface area is 5 ⁇ l OOmVg, preferably 5 ⁇ 30 m 2 /g.
  • the anhydrous magnesium chloride is added to the tetrahydrofuran-alcohol mixture system to form a solution, and the stirring temperature is increased to help shorten the dissolution process, and the temperature ranges from 0 to 60 Torr, preferably 40 to 50 ° C:.
  • the composite support is chemically modified with mercaptoaluminoxane to obtain a modified composite support; a non-metallocene olefin polymerization catalyst having the following structure is dissolved in a solvent:
  • composite carrier, modified composite carrier and supported non-metallocene catalyst replica carrier form are both dry, flowable solid powders.
  • Embodiment 1-1-1 is basically the same as Embodiment 1-1, but with the following changes:
  • the magnesium fluoride was dissolved in a tetrahydrofuran-methanol mixed system to form a solution.
  • Example 1-1-2 the same as Example 1-1, but with the following changes:
  • Examples 1-1-3 are the same as those of the embodiment 1-1, but with the following changes:
  • Embodiments 1-1-4 are basically the same as Embodiment 1-1, but with the following changes:
  • the chemical activator uses a metal halide zirconium chloride; the activated carrier is reacted with zirconium chloride, filtered, washed and dried to obtain a modified carrier.
  • the mass ratio of zirconium chloride to silicon dioxide is 1:
  • Example 1-1-5 with the embodiment 1-1 base «the same, but with the following changes:
  • Examples 1-1-6 are the same as those of the embodiment 1-1, but with the following changes:
  • the chemical activator uses a metal halide zirconium bromide; the activated support is reacted with zirconium bromide, filtered, washed and dried to obtain a modified support.
  • the mass ratio of zirconium bromide to silicon dioxide is 1: Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
  • Embodiments 1-1-7 are basically the same as Embodiment 1-1, but with the following changes:
  • the chemical activator uses a metal halide aluminum fluoride; the activated carrier is reacted with aluminum fluoride, filtered, washed and dried to obtain a modified carrier.
  • the mass ratio of aluminum fluoride to silicon dioxide is 1:
  • the embodiment 1-2 is the same as the embodiment 1-1, but has the following changes:
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the thermal activation condition of the carrier silica is: 100-1000 ° C, under reduced pressure, dried or calcined for 2 ⁇ 12 h;
  • the mass ratio of magnesium chloride to silicon dioxide is 1: 0. 1;
  • the chemical activator uses titanium tetrachloride
  • the thermally activated silica is reacted with the titanium tetrachloride solution for a certain period of time, it is washed and dried by filtration to obtain a modified carrier.
  • the reaction time of silica and titanium tetrachloride solution affects the content of titanium tetrachloride on the surface of silica. Long-term reaction will result in a silica carrier with a high content of titanium tetrachloride. In a short time, the opposite is true. .
  • the superior result can be obtained from 0.5 to 24 hours, and the optimum is to use the reaction for l ⁇ 6h.
  • the temperature is not limited here, but it is obvious that at lower temperature conditions, the amount of loss of titanium tetrachloride from the reaction system due to vaporization is small, which is advantageous for the titanium tetrachloride on the silica carrier. Load efficiency, increase the content of titanium tetrachloride.
  • the high titanium tetrachloride content will help to increase the catalytic olefin polymerization activity of the catalyst, but in the actual operation process, it is not easy to increase the content of titanium tetrachloride, and generally needs to be at a low temperature for a long time.
  • titanium tetrachloride is used to soak the carrier, or multiple times to soak the carrier.
  • the titanium tetrachloride solution can be any titanium tetrachloride and solvent mixture which can form stable properties and uniform properties with titanium tetrachloride.
  • a solution of titanium tetrachloride in hexane was chosen. Filtering the washing solvent to select the pit solvent;
  • the dried modified silica support is a dry flowable powder.
  • the tetrahydrofuran-ol mixed system is changed to tetrahydrofuran-cycloalcohol, and this embodiment is tetrahydrofuran-cyclohexanol;
  • the dissolved magnesium compound is changed to alkoxymagnesium halide, this embodiment is MgC10CH 3 ; the modifier for chemically modifying the composite carrier is changed to alkyl aluminum, for example: trimethyl aluminum, triethyl aluminum, triisobutyl Base aluminum and so on.
  • Example 1-2-1 which is the same as Example 1 but with the following changes:
  • the magnesium compound was changed to MgC10CH 2 CH 3 ;
  • Embodiment 1-2-2 is basically the same as Embodiment 1-2, but with the following changes:
  • the magnesium compound was changed to MgC10C 4 H 9 ;
  • Embodiment 1-2-3 is basically the same as Embodiment 1-2, but with the following changes:
  • the magnesium compound was changed to M g BrOCH 3 .
  • Example 1-2-4 is basically the same as Embodiment 1-2, but with the following changes:
  • Example 1-2-5 is basically the same as Embodiment 1-2, but with the following changes:
  • Embodiment 1-3 is basically the same as Embodiment 1-1, but with the following changes:
  • the thermal activation conditions of the supported silica are: drying or calcination in an Ar atmosphere for 1 to 24 hours; the mass ratio of magnesium chloride to silicon dioxide is 1:10.
  • Examples 1-4 are substantially the same as those of Examples 1-1 to 1-3, but with the following changes: Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier; The mass ratio to silica is 1:1.
  • Embodiments 1-5 are basically the same as Embodiments 1-1 to 1-3, but with the following changes:
  • the composite support reacts directly with the non-metallocene olefin polymerization catalyst and does not act with a chemical treatment agent, and does not require a modified composite support.
  • Examples 1-6 which are basically the same as Examples 1-1 to 1-3, but have the following two changes: Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier; Shield of magnesium chloride and silica The ratio is 1:1;
  • Embodiments 1-7 are basically the same as Embodiments 1-1 to 1-3 or 1-4 - 1-6, but with the following changes:
  • the porous solid as a carrier is changed to: solid inorganic oxides or halides of lanthanum, cerium, group wa and group IVB metal oxides, such as: alumina, magnesia, titania, zirconia, cerium oxide, magnesium chloride.
  • Embodiments 1-8 are basically the same as Embodiments 1-1 to 1-3 or 1-4 to 1-6, but with the following changes:
  • the chemical treatment agent for preparing the modified composite carrier is changed to: a mixture of methyl aluminoxane and titanium tetrachloride;
  • the tetrahydrofuran-alcohol mixed system is changed to tetrahydrofuran-aromatic alcohol, for example: tetrahydrofuran-phenylmethanol, tetrahydrofuran-phenylethanol, tetrahydrofuran-phenylbutanol, tetrahydrofuran-naphthylsterol, tetrahydrofuran-naphthylethanol, tetrahydrofuran-naphthyl Butanol, etc.;
  • the dissolved magnesium compound is changed to: alkoxymagnesium, for example, Mg (0CH 3 ) 2 , Mg (0 CH 2 CH 3 ) 2 , Mg (OC 4 H 9 ) 2 or the like.
  • the preparation examples of the supported non-metallocene olefin polymerization catalyst further include the following examples.
  • Example 1-1 the loading method of the high activity composite support supported non-metallocene catalyst mainly comprises the following steps.
  • modified carrier 2 g of superheat-activated ES70 silica was weighed, stirred with 40 ml of toluene, and then added with 10 ml of TiCl 4 (5 v/v% TiCl 4 in hexane), and reacted at 20 Torr for 16 hr. It was washed with 20 ml of X 3 toluene, filtered, and finally vacuum dried to give a modified carrier.
  • the water content of magnesium chloride should be less than 1% by mass, the average particle size is 30 ⁇ m, and the specific surface area is 25 mVg.
  • the preparation process of the composite carrier should be fully reacted to form a transparent system under stirring at 50 °C. The time is 4 hours.
  • the non-metallocene catalyst was added to a solvent of 1.52 ml of tetrahydrofuran (THF), heated to 50 ° C and completely dissolved. Then, 4 g of the modified composite carrier was added, and the mixture was stirred for 2 hours, then allowed to stand for 12 hours, and then vacuum dried to obtain a supported non-metallocene. catalyst.
  • THF tetrahydrofuran
  • composite carrier, modified composite carrier and supported non-metallocene catalyst replication carrier form are dry, flowable solid powders.
  • the catalyst was recorded as CAT 1-1.
  • the polymerization process using CAT 1-1 is: Ethylene homopolymerization: 50 mg of supported catalyst, 5 ml of cocatalyst decyl aluminoxane (MA0) solution (concentration of 10 wt%) and 5 L of hexane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 250 rpm. Ethylene homopolymerization was carried out at 50 ° C under the polymerization pressure of 2.0 MPa. Drying gave 735 g of polymer.
  • MA0 cocatalyst decyl aluminoxane
  • Embodiment 1-1-1 is basically the same as Embodiment 1-1, but with the following changes:
  • the chemical activator uses titanium fluoride
  • the thermally activated support is reacted with titanium fluoride, filtered, washed and dried to obtain a modified carrier.
  • the cesium fluoride was dissolved in a tetrahydrofuran-methanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-1.
  • Example 1-1- 2 which is basically the same as Example 1-1, but with the following changes:
  • Silica was calcined with ES70X for 8 hours under a nitrogen atmosphere of 500;
  • the chemical activator uses titanium bromide
  • the activated carrier is reacted with titanium bromide, filtered, washed and dried to obtain a modified carrier.
  • the magnesium iodide is dissolved in a tetrahydrofuran-propanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-2.
  • Embodiments 1-1-3 are basically the same as Embodiment 1-1, but with the following changes:
  • the silica crucible is calcined with Grace 948 under an argon atmosphere at 600 Torr for 6 hours; the chemical activator is titanium iodide;
  • the activated carrier is reacted with titanium iodide, filtered, washed and dried to obtain a modified carrier.
  • the magnesium bromide is dissolved in a tetrahydrofuran-butanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-3.
  • Example 1-1-4 substantially the same as Example 1-1, but with the following changes: Silica using Grace SP9-485, calcined in a nitrogen atmosphere at 700 ° C for 5 hours; chemical activator using zirconium chloride;
  • the activated carrier is reacted with zirconium chloride, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride is dissolved in a tetrahydrofuran-pentanol mixed system to form a solution.
  • the catalyst is recorded as CAT 1-1-year
  • Example 1-1 The polymerization process was the same as that in Example 1-1 using CAT 1-1.
  • Examples 1-1-5 were substantially the same as in Examples I-1 except that the silica was used in Grace SP9-10046 in an argon atmosphere at 800. Calcined at C for 4 hours; the chemical activator is zirconium fluoride;
  • the activated carrier is reacted with zirconium fluoride, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-5.
  • Example 1-1-6 substantially the same as Example 1-1, but with the following changes: Silica was prepared by EP10X under a nitrogen atmosphere at 600 Torr for 6 hours;
  • the chemical activator uses zirconium bromide
  • the activated carrier is reacted with zirconium bromide, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
  • Catalyst is recorded as CAT Il-6 0
  • Example 1-1-7 which is basically the same as Example 1-1, but with the following changes: Silica is CS-2133, calcined in a nitrogen atmosphere at 300 ° C for 18 hours; chemical activator is cesium iodide;
  • the activated carrier is reacted with zirconium iodide, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-7.
  • Example 1-1 The polymerization process was the same as that in Example 1-1 using CAT 1-1.
  • Examples 1-1-8 which are basically the same as those of Example 1-1, but have the following changes: Silica is MS- 3040, calcined under a nitrogen atmosphere at 1000 Torr for 1 hour; chemical activator is aluminum chloride;
  • the activated carrier is reacted with aluminum chloride, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride is dissolved in a tetrahydrofuran-heptanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-8.
  • Example 1-1 The polymerization process was the same as that in Example 1-1 using CAT 1-1.
  • Examples 1 to 9 were substantially the same as those of Example 1-1 except that the silica was hollow silica, dried under a nitrogen atmosphere at 100 TC for 24 hours; and the chemical activator was aluminum bromide;
  • the activated carrier is reacted with aluminum bromide, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride was dissolved in a tetrahydrofuran-ethanol mixed system to form a solution.
  • Catalyst is recorded as CAT 1-1-9 D
  • Example 1-1 The polymerization process was the same as that in Example 1-1 using CAT 1-1.
  • Examples 1-1-10 substantially the same as Example 1-1, but with the following changes:
  • the chemical activator is aluminum iodide;
  • the activated carrier is reacted with aluminum iodide, filtered, washed and dried to obtain a modified carrier.
  • Magnesium chloride was dissolved in a tetrahydrofuran-ethanol mixed system to form a solution.
  • the catalyst was recorded as CAT 1-1-10.
  • Embodiment 1-2 is basically the same as Embodiment 1-1, but with the following changes:
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the thermal activation condition of the carrier silica is: 600 Torr, calcined for 6 h under a nitrogen atmosphere; mass ratio of lanthanum chloride to silica is 1:0.
  • the chemical activator uses titanium tetrachloride
  • the dried modified silica support is a dry flowable powder.
  • the catalyst was recorded as CAT 1-2.
  • the dissolved magnesium compound is changed to MgC10CH 3 ;
  • Example 1-2-1 which is basically the same as Example 1-2, but with the following changes: The tetrahydrofuran-ol mixed system is changed to tetrahydrofuran-cyclopentanol;
  • the magnesium compound was changed to MgC10CH 2 CH 3 ;
  • the modifier which chemically modified the composite carrier was changed to trimethylaluminum.
  • the catalyst was changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-2-1.
  • Example 1-2- 2 substantially the same as Example 1-2, but with the following changes:
  • the tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclooctyl alcohol;
  • the magnesium compound was changed to M g C10C 4 H 9 ;
  • the modifier which chemically modified the composite carrier was changed to triisobutylaluminum.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-2-2.
  • Example 1-2-3 was substantially the same as Example 1-2 except that the magnesium compound was changed to MgBrOCH 3 ;
  • the catalyst was changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-2-3.
  • Example 1-2-4 was substantially the same as Example 1-2 except that the magnesium compound was changed to MgBrOCH 2 CH 3 .
  • the catalyst is changed to a compound having the following structural formula:
  • the catalyst is recorded as CAT 1-2-4
  • the polymerization process was the same as the polymerization process using CAT 1-1 in Example 1-1.
  • Examples 1-2 - 5 were substantially the same as those of Example 1-2 except that the magnesium compound was changed to M g BrOC 4 H 9 .
  • the catalyst was recorded as CAT 1-2-5.
  • Embodiments 1-3 are basically the same as Embodiment 1-1, but with the following changes:
  • the thermal activation conditions of the supported silica are: drying or calcination under an argon atmosphere for 8 hours; mass ratio of magnesium chloride to silica is 1:10.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-3.
  • Embodiments 1-4 are basically the same as Embodiment 1-1, but with the following changes:
  • Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier
  • the mass ratio of magnesium to silica is 1:1.
  • the hydrocarbon polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-4.
  • Embodiments 1-5 are basically the same as Embodiment 1-1, but with the following changes:
  • the composite carrier is directly reacted with the non-metallocene olefin polymerization catalyst, does not react with the chemical treatment agent, and does not need to be a modified composite carrier.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-5.
  • Example 1-6 which is basically the same as Example 1-1, but has the following two changes: Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier; the mass ratio of magnesium chloride to silica is 1: 1;
  • the composite carrier is directly reacted with the non-metallocene olefin polymerization catalyst, does not react with the chemical treatment agent, and does not need to be a modified composite carrier.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 1-6.
  • Embodiments 1-7 are basically the same as Embodiment 1-1, but with the following changes:
  • the carrier uses magnesium oxide.
  • the catalyst was recorded as CAT 1-7.
  • ES70 type silica (Crosfield product) was fluidized and activated at a constant temperature of 6 h under a nitrogen atmosphere of 650 TC.
  • the analytical pure magnesium chloride was calcined at 500 ° C for 3 h to obtain anhydrous cesium chloride.
  • Under a nitrogen atmosphere water and oxygen content are less than 5 pp m ), weigh 3 g of anhydrous magnesium chloride, add 60 ml of refined tetrahydrofuran (THF), then add 2.5 ml of refined anhydrous ethanol, and then add 3 g of heat activated
  • the ES70 carrier was stirred for 18 hours at 20 ° C.
  • Example 2-1 The non-metallocene catalyst in THF was subjected to an equal volume impregnation, and finally vacuum dried to obtain a supported non-metallocene catalyst, and the catalyst was designated as CAT1.
  • Example 2-1 The non-metallocene catalyst in THF was subjected to an equal volume impregnation, and finally vacuum dried to obtain a supported non-metallocene catalyst, and the catalyst was designated as CAT1.
  • Example 2-2 a non-metallocene catalyst in toluene was added, and the reaction was stirred for 16 hours at .20, mixed. The combined liquid was washed with 30 ml of x 3 benzene, filtered, and vacuum dried to obtain a catalyst precursor. The catalyst precursor was weighed 0.5 g, and an isocratic immersion solution of 0 ⁇ 125 g of a non-metallocene catalyst was added thereto, and uniformly stirred, and uniformly dried, and vacuum-dried to obtain a supported non-metallocene catalyst, and the catalyst was recorded as CAT2.
  • Example 2-2 An isocratic immersion solution of 0 ⁇ 125 g of a non-metallocene catalyst was added thereto, and uniformly stirred, and uniformly dried, and vacuum-dried to obtain a supported non-metallocene catalyst, and the catalyst was recorded as CAT2.
  • Example 2-2
  • Ethylene homopolymerization Simultaneously add 46 mg of supported catalyst CAT2, 8 ml of MAO solution (concentration of 15 wt%) and 5 L of hexane solvent in a 10 L batch polymerization reactor, and start stirring at 250 rpm, and pass ethylene to polymerization pressure 2 0 MPa, ethylene homopolymerization was carried out, and the reaction time was 3 h.
  • Example 2-3 Simultaneously add 46 mg of supported catalyst CAT2, 8 ml of MAO solution (concentration of 15 wt%) and 5 L of hexane solvent in a 10 L batch polymerization reactor, and start stirring at 250 rpm, and pass ethylene to polymerization pressure 2 0 MPa, ethylene homopolymerization was carried out, and the reaction time was 3 h.
  • Ethylene hydrogenation polymerization To a 2L autoclave, 31.2 mg of supported catalyst CAT2, 3. lml of MAO in toluene solution (concentration of 15 wt%) and 1 L of hexane were added, the stirring speed was 500 rpm, and the polymerization pressure was maintained at 2.0 MPa. The hydrogen pressure was 0.1 MPa, and the ethylene polymerization was carried out under hydrogenation at 50 Torr. The reaction time was 2 h.
  • Example 2-4 To a 2L autoclave, 31.2 mg of supported catalyst CAT2, 3. lml of MAO in toluene solution (concentration of 15 wt%) and 1 L of hexane were added, the stirring speed was 500 rpm, and the polymerization pressure was maintained at 2.0 MPa. The hydrogen pressure was 0.1 MPa, and the ethylene polymerization was carried out under hydrogenation at 50 Torr. The reaction time was 2 h.
  • Example 2-4 To a 2L autoclave, 31.2 mg of
  • the propylene is fed into the ethylene.
  • the polymerization is carried out at a pressure of 500 rpm.
  • the polymerization pressure is 2.0 MPa.
  • butene-1 40 g was added, and ethylene and 1-butene were copolymerized at 50 Torr for 2 hours.
  • Example 2-6
  • the singularity of the polymerization is 2. MPa, the polymerization is carried out at a pressure of 500 rpm, the stirring pressure is 500 rpm, and the polymerization pressure is 2.0 MPa. After 5 minutes of ethylene, 30 g of 1-hexene was added, and ethylene and 1-hexene were copolymerized at 50 ° C for 2 hours.
  • Ethylene homopolymerization In a 2L autoclave, 26 mg of supported catalyst CAT3, 2.6 ml of MA0 in benzene solution (concentration of 10 wt%) and 1 L of hexane were added simultaneously, the stirring speed was 500 rpm, and ethylene was fed to the polymerization pressure 2 0MPa Ethylene homopolymerization was carried out at 50 Torr for a reaction time of 2 h.
  • Ethylene homopolymerization In a 2 L autoclave, 16. Omg of supported catalyst CAT3, 3.2 ml of TiBA in hexane solution (15 wt% /.) and 1 L of hexane were added, and the stirring speed was 250 rpm, and ethylene was fed to the polymerization pressure. 2. 0 MPa, ethylene homopolymerization at 70 Torr, reaction time 2 hr.
  • the propylene, the polymerization pressure is 2.0 MPa, and the polymerization is carried out at a pressure of 500 rpni, a polymerization pressure of 2.0 MPa, and a polymerization rate of 2.0 MPa.
  • After 13 minutes of ethylene 40 g of propylene monomer was added, and ethylene and propylene were copolymerized at 5 (TC) for 2 h.
  • Example 2-15
  • Ethylene homopolymerization 18.8 mg of supported catalyst CAT3 was added simultaneously in a 2 L autoclave, and tributylammonium tetrakis(pentafluoroboron)boron and 1 L of hexane were added in a molar ratio of boron to titanium, and the stirring speed was 500 rpm. Ethylene was homopolymerized at a polymerization pressure of 2.0 MPa at 50 ° C for a reaction time of 2 hr. Stop the reaction.
  • Ethylene copolymerization 20.2 mg of supported catalyst CAT3, 2. 0 ml of MA0 in toluene solution (concentration of 10 wt%) and 1 L of hexane were added to a 2 L autoclave at a stirring speed of 300 rpm. The polymerization pressure was 2.0 MPa. After 13 minutes of ethylene addition, 40 g of 1-octene monomer was added, and ethylene and octene were copolymerized at 50 ° C for 2 h. Stop the reaction.
  • the silica was changed to ES757.
  • the catalyst was recorded as CAT ⁇ -1.
  • Ethylene homopolymerization 50 mg supported catalyst, 5 ml cocatalyst triethylaluminum (TEA) solution (concentration: 15 wt%) and 5 L of hexane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 250 rpm. Ethylene was homopolymerized at a polymerization pressure of 2. OMPa. After drying, 770 g of a polymer was obtained.
  • TSA cocatalyst triethylaluminum
  • Copolymerization of ethylene and butene 40 mg of supported catalyst, 28 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of decane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 400. 5MPa, rpm, adding hydrogen to 0. 3MPa, Then, ethylene was introduced to a polymerization pressure of 0.2 MPa, and after 5 minutes, a pump such as 40 g of butene was subjected to copolymerization of ethylene and butene at 80 Torr. 5 2 0g dried to obtain a polymer.
  • TSA cocatalyst triethylaluminum
  • Copolymerization of ethylene and hexene 20 liters of supported catalyst, 25 ml of cocatalyst triisobutylaluminum (IBAL) solution (concentration of 15 wt%) and 5 L of octane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 400. After rpm, hydrogen was added to 0.3 MPa, and then ethylene was introduced to a polymerization pressure of 0.85 MPa. After 5 minutes, 20 g of hexene was pumped, and ethylene and hexene copolymerization was carried out at 60 °C. After drying, 92 g of a polymer was obtained.
  • IBAL cocatalyst triisobutylaluminum
  • Copolymerization of ethylene and precipitation olefin In a 10L high pressure polymerization reactor, 120mg of supported catalyst, 24ml of cocatalyst ethylaluminoxane (EA0) solution (concentration of 15wt%) and 5L of ethylbenzene solvent were added simultaneously to open the stirring speed. After 100 rpm, ethylene was introduced to a polymerization pressure of 0.60 MPa, and after 5 minutes, 30 g of norbornene was pumped, and ethylene and norbornene copolymerization was carried out at 1201:. After drying, 888 g of a polymer was obtained.
  • EA0 cocatalyst ethylaluminoxane
  • Copolymerization of ethylene and decyl methacrylate In a 10 L high pressure polymerization reactor, 2. 05 g of supported catalyst, 1400 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of p-xylene solvent were simultaneously added. The stirring speed was 500 rpm, and then ethylene was fed to a polymerization pressure of 0.40 MPa. After 5 minutes, 100 g of decyl methacrylate was pumped, and ethylene and methacrylate methacrylate copolymerization was carried out at 110 °C. After drying, 2460 g of a polymer was obtained.
  • TEA cocatalyst triethylaluminum
  • Co-polymerization of acetamidine and propylene In a 10L high-pressure polymerization reactor, simultaneously add 72nig supported catalyst, 2ml of trimethylammonium tetraphenylboron solution (concentration of 15g/L) and 5L of hexane solvent, and the stirring speed is 150. At rpm, ethylene was fed to a polymerization pressure of 0 ⁇ 85 MPa, and after 5 minutes, 60 g of propylene was pumped, and ethylene and propylene were copolymerized at 80 °C. After drying, 388 ⁇ 8 g of a polymer was obtained.
  • Copolymerization of ethylene and octene In a 10 L high pressure polymerization reactor, 276 mg of supported catalyst, 1 ml of trimethylphosphine tetraphenylboron solution (concentration of 10 g / L) and 5 L of hexane solvent were added simultaneously, and the stirring speed was started. 150 rpm, pumping 45g of octene after 5 minutes, then Ethylene was fed to a polymerization pressure of 0.85 MPa, and ethylene and octene were copolymerized at 80 Torr. After drying, 883. 2 g of a polymer was obtained.
  • Ethylene homopolymerization In a 10 L high pressure polymerization reactor, 164 mg of supported catalyst, 5 m of triisobutylboron solution (concentration of 20 g/L) and 5 L of hexane solvent were added simultaneously, and the stirring speed was 150 rpm, and ethylene was introduced. The polymerization was carried out at a polymerization pressure of 0.885 MPa at 801. After drying, 1262 ⁇ 8 g of a polymer was obtained.
  • Copolymerization of ethylene and styrene 40 mg of supported catalyst, 28 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of hexane solvent were added simultaneously in a 10 L high pressure polymerization reactor, and the stirring speed was 400. After rpm, ethylene was introduced to a polymerization pressure of 0.85 MPa, and after 5 minutes, 40 g of styrene was pumped, and ethylene and styrene were copolymerized at 80 Torr. After drying, 64 g of a polymer was obtained.
  • TSA cocatalyst triethylaluminum
  • Copolymerization of ethylene and styrene under hydrogen adjustment 40 mg of supported catalyst, 28 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of hexane solvent were added simultaneously in a 10 L high pressure polymerization reactor to open the stirring speed. To 400 rpm, hydrogen was added to 0.3 MPa, and ethylene was introduced to a polymerization pressure of 0.85 MPa. After 5 minutes, 40 g of styrene was pumped in, and ethylene and styrene were copolymerized at 80 °C. After drying, 44 g of a polymer was obtained.
  • TSA cocatalyst triethylaluminum
  • Ethylene homopolymerization 200 nig supported catalyst, 20 ml of triethylaluminum (concentration: 15 wt%), 0.2 L of hexane solvent, and 100 g of anhydrous sodium chloride were added simultaneously in a 10 L high pressure gas phase polymerization reactor to open the stirring speed. At 50 rpm, ethylene was fed to a polymerization pressure of 2.0 MPa, and ethylene gas phase homopolymerization was carried out at 80 Torr. After drying to remove sodium chloride, 680 g of a polymer was obtained.
  • Copolymerization of ethylene and hexene 200 mg of supported catalyst, 20 ml of triethylaluminum (concentration: 15 wt%), 0.2 L of hexane solvent, and 100 g of anhydrous sodium chloride were simultaneously added to a 10 L high pressure gas phase polymerization reactor.
  • the stirring speed was 50 rpm, ethylene was fed to a polymerization pressure of 2. OMPa, and after 5 minutes, 50 g of hexene was added, and ethylene and hexene gas phase copolymerization was carried out at 80 Torr. After drying to remove sodium chloride, 540 g of a polymer was obtained.
  • the catalyst was recorded as CAT ⁇ -2.
  • Silica is changed to a polystyrene carrier having a carboxyl group on the surface, and dried at 100" C for 24 hours under nitrogen;
  • the chemical activator uses titanium fluoride
  • the catalyst was recorded as CAT ⁇ -3.
  • Silica is changed to zirconia support, calcined at 500 Torr for 8 hours under nitrogen; chemical activator is titanium bromide;
  • the catalyst was recorded as CAT ⁇ -4.
  • the silica is changed to a titanium oxide carrier, and calcined at 40 (TC, nitrogen for 2 hours; the chemical activator is made of metal
  • the catalyst was recorded as CAT ⁇ -5.
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -1 catalyst.
  • Example II-6 The ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -1 catalyst.
  • the silica was changed to a porous clay and dried at 100 ° C for 12 hours under nitrogen; the chemical activator was a metal halide zirconium chloride;
  • the catalyst was recorded as CAT ⁇ -6.
  • the ethylene homopolymerization process is the same as the polymerization process using a CAT ⁇ -1 catalyst.
  • the silica is changed to a kaolin carrier and dried under nitrogen at 150 ° for 24 hours;
  • the chemical activator is a metal halide zirconium fluoride;
  • the catalyst was recorded as CAT ⁇ -7.
  • the silica is changed to a diatomaceous earth carrier and dried at 250 ° C for 16 hours under nitrogen;
  • the chemical activator is a metal
  • the catalyst was recorded as CAT ⁇ -8.
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -1 catalyst.
  • the silica was changed to a polyvinyl chloride carrier and dried under nitrogen at 10 C for 12 hours;
  • the chemical activator uses a metal 13 ⁇ 4 compound zirconium iodide;
  • the catalyst was recorded as CAT ⁇ -9.
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -1 catalyst.
  • the silica was changed to a polymethacrylate carrier and dried at 150 Torr for 8 hours under nitrogen;
  • the chemical activator uses a metal halide aluminum fluoride
  • the catalyst was recorded as CAT ⁇ - 10.
  • Silica was changed to a mixed carrier of silica and titania, and calcined at 400 TC for 8 hours under nitrogen;
  • the chemical activator uses a metal halide aluminum bromide
  • the catalyst was recorded as CAT ⁇ - 11.
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -1 catalyst.
  • the silica is changed to a composite carrier of silica and magnesium bromide, wherein the silica is calcined at 400 ° C for 12 hours under nitrogen;
  • the chemical activator is made of metal
  • the catalyst was recorded as CAT ⁇ -12.
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -l catalyst.
  • the silica was changed to a bentonite carrier and dried at 200 Torr for 8 hours under nitrogen; Catalyst is recorded as CAT ⁇ -13 ⁇
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -1 catalyst.
  • the silica is changed to a mixed carrier of magnesium oxide and zirconium oxide, and the mixed carrier is calcined at 450 C under nitrogen for 6 hours;
  • the catalyst was recorded as CAT ⁇ -14.
  • the ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -l catalyst.
  • Example 11-15 The ethylene homopolymerization process is the same as the polymerization process using CAT ⁇ -l catalyst.
  • Silica was changed to MCM-41 molecular sieve carrier and calcined under nitrogen for 4 hours;
  • the catalyst was recorded as CAT ⁇ -15.
  • the silica was changed to a mixed carrier of silica and montmorillonite, and the mixed carrier was calcined at 200 ° C for 12 hours under nitrogen;
  • the catalyst was recorded as CAT ⁇ -16.
  • the ethylene homopolymerization process is the same as the polymerization process using a CAT ⁇ -1 catalyst.
  • the thermal activation conditions of the silica were calcined under nitrogen at 400 ° C for 8 hours.
  • the catalyst was recorded as CAT ⁇ -17.
  • the ethylene homopolymerization process is the same as the polymerization process using a CAT®-l catalyst.
  • the thermal activation conditions of the silica were calcined under argon at 200 Torr for 12 hours.
  • the catalyst was recorded as CAT ⁇ -18.
  • the thermal activation conditions of the silica were dried under nitrogen, 100 ° C for 24 hours, and the catalyst was designated as CAT ⁇ -19.
  • the ethylene homopolymerization process is the same as the polymerization process using a CAT ⁇ -1 catalyst.
  • Example 3-1 the supported non-metallocene olefin polymerization catalyst of the present invention was prepared and used in slurry polymerization of ethylene.
  • ES70 type silica (product of Ineos) was calcined under a nitrogen atmosphere. The firing conditions are: heating rate 5. C / Min, constant temperature at 200 ° C 0. 5h, constant temperature at 400 ° C 0. 5h, then constant temperature at 600 ° C for 4h, and finally cooled naturally under nitrogen atmosphere. Recorded as ES70-650 carrier.
  • Anhydrous magnesium chloride was prepared by calcining pure magnesium chloride at 500 C in an air atmosphere for 3 hours. Under an anhydrous and oxygen-free nitrogen atmosphere (water and oxygen contents are less than 5 ppm), 10 g of anhydrous magnesium chloride is weighed, 200 ml of tetrahydrofuran is added, and 25 ml of absolute ethanol (3A molecular sieve soaked for 4 days) is added dropwise. After the magnesium chloride was completely dissolved, the above carrier was further added, stirred at 50 for 4 hours, filtered, washed three times with 240 ml of toluene, finally dried and vacuum dried to give 19.9 g of a composite carrier.
  • the catalyst was recorded as CAT-1.
  • the supported non-metallocene catalyst and the cocatalyst constitute a catalytic system and are directly used for the polymerization of ethylene slurry.
  • hydrogen is used as a chain transfer agent in the polymerization process.
  • the amount of hydrogen used may be 0.011. 99 (volume ratio) of the total gas amount.
  • the solvent involved in this example is hexane.
  • this embodiment adopts the suction filtration method: the system to be washed and filtered is put into the sand core funnel, the solvent is removed by suction filtration, and then the solvent is added, and then filtered, thereby washing.
  • the washing and filtering process is preferably repeated 2 to 4 times.
  • the solid is dried under reduced pressure at a temperature of about 0 to 120 Torr until a fluid catalyst carrier powder is obtained.
  • the length of this drying process depends on the temperature used and the capacity of the vacuum system and the containment of the system.
  • anhydrous anaerobic conditions refer to the water and oxygen contents in the system.
  • anhydrous anaerobic conditions are one of the key factors in obtaining a highly active supported catalyst.
  • Adequate washing filtration, dry drying, and drying are also key to achieving high activity and good particle morphology.
  • the washing and filtering process removes the free matter, and drying and drying can obtain a good binding force of the reaction substance.
  • Example 3 - 2
  • silica is ES70X, and the catalyst is recorded as CAT-2;
  • Example 3-3 The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as in Example 1, except that the cocatalyst was selected from ethylaluminoxane (EA0).
  • EA0 ethylaluminoxane
  • the silica was ES70Y, and the catalyst was recorded as CAT-3.
  • the catalyst is selected from isobutyl aluminoxane ( IBA0 );
  • the solvent of this embodiment is tetrahydrofuran
  • the silica is hollow silica, and the catalyst is referred to as CAT-4;
  • the carrier is a mixture of alumina and silica (the mass ratio of alumina to silica is 1: 2 );
  • the catalyst was prepared by replacing 2 ml of MAO (10 wt% in toluene solution) with 20 ml of MAO (10 wt% in toluene solution);
  • Magnesium chloride is changed to a mixture of magnesium chloride and ethoxymagnesium chloride (magnesium chloride and ethoxylated magnesium chloride must be 4:1).
  • the chemical treatment agent is selected from triethyl aluminum (TEA);
  • the solvent for catalyst preparation is pentane.
  • the support is silica obtained by hydrolysis of SiH 4 through its phase.
  • the catalyst was prepared by replacing 20 ml of MA0 (10 wt% in toluene solution) with 20 ml of triethylaluminum (0.43 mol/l hexane solution), and the catalyst was designated as CAT-6.
  • the support is polystyrene and the surface has an ethoxy functional group.
  • the modified composite carrier does not use methylaluminoxane; when the non-metallocene catalyst is loaded, 5g is modified.
  • the carrier was impregnated with a solution of 1.5 g of a non-metallocene catalyst in 20 ml of tetrahydrofuran and directly drained. The carrier selects alumina.
  • the solvent for catalyst preparation is flawed.
  • the carrier is a polyolefin carrier.
  • the modified composite carrier was replaced with 2 ml of MA0 (10 wt% benzene solution) in 20 ml of MAO (10 wt% toluene solution); when the non-metallocene catalyst was supported, 5 g of the modified composite carrier and 1.5 g of the non-metallocene catalyst were impregnated with 20 ml of the benzene solution. dry.
  • the carrier is CS-2133 type silica.
  • the preparation of the catalyst was carried out by substituting 39 ml of butanol for 25 ml of ethanol in addition to the preparation of the composite carrier; the solvent for catalyst preparation was dichloroethane.
  • the preparation of the catalyst is in addition to the structural formula.
  • the remainder of the metallocene catalyst was the same as in Example 3-1.
  • the carrier is not thermally activated and acts directly with the chemical activating agent to obtain a modified carrier.
  • the solvent for catalyst loading is diphenylbenzene.
  • the composite support is directly reacted with a non-metallocene olefin polymerization catalyst and has not previously been treated with a chemical treatment agent.
  • the solvent for catalyst preparation was tetrahydrofuran.
  • the catalyst was recorded as CAT-16.
  • Example III-1 the supported non-metallocene olefin polymerization catalyst of the present invention was further prepared and used in slurry polymerization of ethylene.
  • Example 1-1 The catalyst preparation process of Example 1-1 is substantially the same, but with the following changes: the preparation of a modified composite carrier: 4g was added to 40ml of benzene Yue composite carrier was added dropwise only 20mlTiCl 4 (5v / v TiCl 4 in hexane) The reaction was stirred at 20 ° C for 2 hours. The mixed solution was washed with 30 ml of hydrazine, filtered, and dried in vacuo to give a modified composite.
  • a modified composite carrier 4g was added to 40ml of benzene Yue composite carrier was added dropwise only 20mlTiCl 4 (5v / v TiCl 4 in hexane) The reaction was stirred at 20 ° C for 2 hours. The mixed solution was washed with 30 ml of hydrazine, filtered, and dried in vacuo to give a modified composite.
  • the catalyst was recorded as CAT ⁇ -1.
  • the cocatalyst is methylaluminoxane (MA0).
  • the supported non-metallocene catalyst and cocatalyst constitute a catalytic system and are directly used for the polymerization of ethylene slurry.
  • 23.4 g of supported catalyst was added to a 10 liter polymerization reactor, then 2.3 ml of methylaluminoxane (MAO) (concentration: 10 wt%) and 5 liters of hexane were added, and polymerization was carried out for 2 hours under a total pressure of 0.8 MPa of ethylene.
  • the speed was 250 rpm and the polymerization temperature was 80 ⁇ .
  • hydrogen is used as a chain transfer agent in the polymerization process.
  • the amount of hydrogen used can range from 0.01 to 0.99 (by volume) of the total gas.
  • silica is ES70X
  • the chemical activator uses A1C1 3 ;
  • the catalyst was recorded as CAT m-2.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment III-1, but the polymerization pressure is 2. OMPa, the polymerization temperature is 501 C, and the promoter is selected from triethyl aluminum (TEA). The amount of gas is 0.4 (volume ratio).
  • Example III-3
  • the silica in the preparation of the catalyst is ES70Y;
  • the chemical activator uses VC1 5 ;
  • the solvent of this embodiment is tetrahydrofuran;
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -3.
  • the polymerization temperature is 4. OMPa, the polymerization temperature is 40, and the polymerization temperature is 2. OMPa, the polymerization temperature is 40, and the polymerization temperature is 4. OMPa, the polymerization temperature is 40.
  • the amount of hydrogen accounts for 0.4 (volume ratio) of the total gas.
  • the silica is hollow silica
  • the chemical activator is triethylaluminum
  • Magnesium chloride is changed to alkoxy! 3 ⁇ 4 mixture of magnesium and alkoxymagnesium.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -4.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment III-1, but the promoter is selected from tridecyl aluminum (ruthenium), the polymerization pressure is 1.5 MPa, the polymerization temperature is 75 ° C, and ethylene and Butene copolymerization, butene was added to 25 g.
  • the promoter is selected from tridecyl aluminum (ruthenium)
  • the polymerization pressure is 1.5 MPa
  • the polymerization temperature is 75 ° C
  • ethylene and Butene copolymerization, butene was added to 25 g.
  • the carrier is a mixture of alumina and silica (the mass ratio of alumina to silica is 1: 2), and the carrier is calcined at 800 Torr for 4 hours under a nitrogen atmosphere;
  • Magnesium chloride is changed to a mixture of magnesium chloride and ethoxymagnesium chloride (magnesium chloride and ethoxylated magnesium chloride must be 4:1).
  • the chemical treatment agent is selected from triethyl aluminum (TEA);
  • the solvent for catalyst preparation is pentane.
  • the catalyst was recorded as CAT ⁇ -5.
  • Example III-6 The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1, but the promoter was selected from triethylaluminoxane (EA0), the polymerization pressure was 2.5 MPa, the polymerization temperature was 40 Torr, and the polymerization solvent was used. Dichloroethane is used.
  • EA0 triethylaluminoxane
  • the support is silica obtained by hydrolysis of SiH 4 through its phase.
  • the chemical activator is triisobutylaluminum
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ - 6.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment 111-1, but the promoter is selected from MA0-TEA, the polymerization pressure is G.7 MPa, the polymerization temperature is 85 ° C, and the amount of hydrogen accounts for the total gas amount. 0.071 (volume ratio).
  • Example III-7
  • the carrier is polystyrene and has a carboxyl functional group on the surface.
  • the chemical activator uses a mercaptoaluminoxane
  • the modified composite carrier does not use fluorenyl aluminoxane; when supported by a non-metallocene catalyst, 5 g of the modified composite carrier is impregnated with a solution of i. 5 g of a non-metallocene catalyst in 20 ml of tetrahydrofuran and directly pumped.
  • the carrier selects alumina.
  • the solvent for catalyst preparation is decane.
  • the catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -7.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also the same as that of the embodiment III-1, but the promoter is selected from MAO-ruthenium, the polymerization pressure is G. 7 MPa, the polymerization temperature is 85 ° C, and the polymerization solvent is heptane. 014 ( ⁇ ) ⁇ The amount of hydrogen in the total amount of gas is 0. 014 (volume ratio).
  • the promoter is selected from MAO-ruthenium
  • the polymerization pressure is G. 7 MPa
  • the polymerization temperature 85 ° C
  • the polymerization solvent is heptane. 014 ( ⁇ ) ⁇
  • the amount of hydrogen in the total amount of gas is 0. 014 (volume ratio).
  • the carrier is a polypropylene carrier having a carboxyl group on its surface.
  • the modified composite support was replaced with 2 ml of MA0 (10 wt% decene solution) in place of 20 ml of MA0 (10 wt% toluene solution); when supported by a non-metallocene catalyst, 5 g of the modified composite support was impregnated with 1.5 g of a non-metallocene catalyst in 20 ml of toluene and directly drained.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -8.
  • the amount of hydrogen in the total amount of gas is 0. 7MPa, the amount of hydrogen in the total amount of gas is the same as that in the embodiment I II-1. 0. 357 (volume ratio).
  • the carrier is CS-2133 type silica.
  • the preparation of the catalyst was carried out by substituting 39 ml of butanol for 25 ml of ethanol in addition to the preparation of the composite carrier; the solvent for catalyst preparation was dichloroethane.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -9.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of Example II-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 2.0 MPa, the polymerization temperature is 65 ° C, and the polymerization is carried out.
  • pentane solvent employed, the copolymerization of ethylene with propylene, propylene was added in an amount of 20g o Example 111-10
  • the polymerization catalyst was changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 11-10.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of Example III-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 0.7 MPa, the polymerization temperature is 9 (TC, and the polymerization solvent is used.
  • TAA triethylaluminum
  • TC polymerization temperature
  • TC polymerization temperature
  • the polymerization solvent is used.
  • the decane was copolymerized with ethylene and hexene, and the amount of hexene added was 10 g.
  • the catalyst was changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT m-ii.
  • Example 111-12 The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1 except that the promoter was selected from triethylaluminum (TEA), the solvent was octane, and the polymerization pressure was 0.7 MPa.
  • TAA triethylaluminum
  • Example 111-12 the promoter was selected from triethylaluminum (TEA), the solvent was octane, and the polymerization pressure was 0.7 MPa.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT m-12.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of Example III-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 2.0 MPa, the polymerization temperature is 75, and the amount of hydrogen accounts for the total gas. The amount is 0.95 (volume ratio).
  • TAA triethylaluminum
  • the catalyst was supported with solvent cyclohexane.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -13.
  • Example ⁇ -14 The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1 except that the polymerization pressure was 2. OMPa, the polymerization temperature was 60 ° C, and the amount of hydrogen was 0.25 (volume ratio) of the total gas.
  • Example ⁇ -14 The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1 except that the polymerization pressure was 2. OMPa, the polymerization temperature was 60 ° C, and the amount of hydrogen was 0.25 (volume ratio) of the total gas.
  • Example ⁇ -14 The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1 except that the polymerization pressure was 2. OMPa, the polymerization temperature was 60 ° C, and the amount of hydrogen was 0.25 (volume ratio) of the total gas.
  • Example ⁇ -14 The slurry polymerization process using the above supported non-metallo
  • a 5 g modified composite support When supported by a non-metallocene catalyst, a 5 g modified composite support was impregnated with a solution of 1.5 g of a non-metallocene catalyst in 100 ml of toluene for 16 hours, filtered, and 120 ml of toluene was washed three times, and finally dried and drained.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT ⁇ -14.
  • Example 111-15 The slurry polymerization process using the above supported non-metallocene catalyst was also the same as in Example III-1 except that the polymerization solvent was selected from toluene and the polymerization pressure was 0.7 MPa.
  • Example 111-15 The slurry polymerization process using the above supported non-metallocene catalyst was also the same as in Example III-1 except that the polymerization solvent was selected from toluene and the polymerization pressure was 0.7 MPa.
  • Example 111-15 Example 111-15
  • the carrier is not thermally activated and acts directly with the chemical activating agent to obtain a modified carrier.
  • the solvent for catalyst loading is xylene.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT III -15.
  • the slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment I II-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 1.0 MPa, and the amount of hydrogen accounts for the total amount of gas. 0.30 (volume ratio), ethylene was copolymerized with heptene, and the amount of heptene added was 50 g.
  • TAA triethylaluminum
  • ethylene was copolymerized with heptene
  • the amount of heptene added was 50 g.
  • the composite support is directly reacted with a non-metallocene olefin polymerization catalyst and has not previously been treated with a chemical treatment agent.
  • the solvent for catalyst preparation was tetrahydrofuran.
  • the non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
  • the catalyst was recorded as CAT 111-16.
  • Example II-1 The slurry polymerization process using the above supported non-metallocene catalyst was also the same as in Example I II-1.
  • the promoter used was tripropylaluminum (TPA)
  • the polymerization pressure was 2.7 MPa
  • the solvent was toluene
  • the polymerization temperature was 95.
  • C copolymerization of ethylene and precipitation borneene
  • the amount of norbornene added was 40 g. Comparative Example II 1-1
  • the carrier does not undergo a chemical activation process
  • the catalyst is recorded as CAT ⁇ -17 ⁇
  • the carrier does not undergo a chemical activation process
  • the catalyst was recorded as CAT ⁇ -18.
  • Catalyst amount (mg) Cocatalyst Polymerization temperature ( 'C ) Solvent for polymerization Polymerization type Polymerization pressure (MPa) Bulk density (g/ml Catalyst (ml) (KgPE/gCat)
  • novel catalysts provided by the present invention also improve the morphology of the polymer; increase the bulk density of the polymer and increase the polymerization activity.
  • the novel structure-based supported non-metallocene catalyst disclosed in the present invention for catalyzing olefin polymerization and/or copolymerization processes, high olefin polymerization activity can be obtained. Meanwhile, the polymer obtained by using the supported non-metallocene olefin polymerization catalyst prepared by the present invention has an excellent particle morphology.
  • the slurry polymerization process requires less methylamoxyoxane, and may even be completely unused.
  • the reaction is stable, the polymerization temperature is easy to control, and there is no sticking phenomenon.
  • the polyolefin obtained by the supported non-metallocene olefin polymerization catalyst prepared by the present invention has an excellent particle morphology, and the polymer bulk density can be up to 0.385 g / liter.

Abstract

A process for deposition of non-metallocene olefin polymerization catalyst on support comprises: reacting support with chemically activating agents to obtain modified support; dissolving magnesium compound in mixed solvent of tetrahydrofuran-alcohol to form a solution, adding said modified support into the solution to react, and filtering, washing and drying under reduced pressure to give a composite support; dissolving non-metallocene olefin polymerization catalyst into solvent and reacting with the composite support, and washing, filtering and drying under reduced pressure to give supported non-metallocene olefin polymerization catalyst. A supported non-metallocene olefin polymerization catalyst is prepared by the process of the present invention, and the catalyst is used for olefin polymerization or copolymerization of two or more different olefins. In a specific embodiment, the said supported non-metallocene olefin polymerization catalyst is used for slurry polymerization of olefin. The new catalyst of the present invention allows to manufacture polymers having improved morphology, increased bulk density and activities.

Description

一种负载型非茂金属烯烃聚合催化剂、 其制备方法及其应用 技术领域  Supported non-metallocene olefin polymerization catalyst, preparation method thereof and application thereof
本发明属于非均相催化剂技术领域， 具体而言， 涉及一种负载型 非茂金属烯烃聚合催化剂的制备方法， 它是一种在载体上负载非茂金 属烯烃聚合催化剂的方法， 以及由该方法所制备的负载型非茂金属烯 烃聚合催化剂。 本发明还涉及该负载型非茂金属烯烃聚合催化剂在催 化烯烃聚合以及两种以上不同烯烃之间进行的共聚中的应用。 在一个 具体实施方案中， 本发明涉及该负载型非茂金属烯烃聚合催化剂在淤 浆法乙烯聚合中的应用， 换言之， 采用本发明的负载型非茂金属烯烃 聚合催化剂进行的低压淤浆法乙烯聚合。 背景技术  The present invention relates to the field of heterogeneous catalyst technology, and in particular to a method for preparing a supported non-metallocene olefin polymerization catalyst, which is a method for supporting a non-metallocene olefin polymerization catalyst on a support, and by the method A supported non-metallocene olefin polymerization catalyst prepared. The invention further relates to the use of the supported non-metallocene olefin polymerization catalyst for the polymerization of olefins and the copolymerization of two or more different olefins. In a specific embodiment, the present invention relates to the use of the supported non-metallocene olefin polymerization catalyst in slurry ethylene polymerization, in other words, low pressure slurry ethylene treatment using the supported non-metallocene olefin polymerization catalyst of the present invention. polymerization. Background technique
已知均相的过渡金属催化剂在烯烃聚合中有很高的催化活性， 如 非负载的齐格勒-纳塔催化剂、 茂金属烯烃聚合催化剂、 限定几何构 型烯烃聚合催化剂或非茂金属烯烃聚合催化剂。 非茂金属烯烃聚合催 化剂的配位原子为氧、 氮、 硫和碳等， 不含有环戊二烯基团， 是二十 世纪九十年代初期发现并得到展开研究的， 其催化活性可以达到甚至 超过茂金属烯烃聚合催化剂， 而且同时保持了茂金属催化体系的聚合 物可控、 分子量分布窄、 可以对聚合物进行分子剪裁、 聚合物分子量 和支化度可以调控等优点， 而且由于此类催化剂亲氧性弱， 可以实现 极性单体与烯烃的共聚， 从而生产出性能优异的功能化聚烯烃材料。  Homogeneous transition metal catalysts are known to have high catalytic activity in olefin polymerization, such as unsupported Ziegler-Natta catalysts, metallocene olefin polymerization catalysts, defined geometry olefin polymerization catalysts or non-metallocene olefin polymerizations. catalyst. The coordination atom of the non-metallocene olefin polymerization catalyst is oxygen, nitrogen, sulfur and carbon, and does not contain a cyclopentadienyl group. It was discovered and developed in the early 1990s, and its catalytic activity can reach even Exceeding the metallocene olefin polymerization catalyst, while maintaining the metallocene catalyst system, the polymer is controllable, the molecular weight distribution is narrow, the molecular cutting of the polymer can be performed, the molecular weight and the degree of branching of the polymer can be regulated, and the like The aerobicity is weak, and the copolymerization of a polar monomer and an olefin can be achieved, thereby producing a functionalized polyolefin material excellent in performance.
均相聚合时， 形成的聚合物会产生粘釜和缠绕搅拌桨的现象， 这 对反应器的正常运转和反应器内物料的热交换有较大的影响， 不利于 工业化的连续生产。 另外， 均相催化体系中需要大量的助催化剂曱基 铝氧烷， 使聚烯烃的生产成本增加， 而且由于大量助催化剂的引入， 对产品性能也产生了不利的影响， 有些甚至需要在后序加工中除去聚 合过程中引入的铝， 进一步增加了过程的成本。 专利 W003/ 010207 所 制备的一种烯烃聚合及共聚合催化剂或催化体系， 具有广泛的烯烃聚 合和共聚性能， 适用于多种形式的聚合工艺， 但在烯烃聚合时需要较 高的助催化剂用量才能获得合适的烯烃聚合活性， 而且聚合过程存在 着粘釜现象。 根据茂金属烯烃聚合催化剂工业化应用的经验（Chem Rev, 2000, 100: 1347; Chem Rev, 2000, 100: 1377 ) ， 均相非茂金属烯烃聚合 催化剂的负载化十分必要。 In the homogeneous polymerization, the formed polymer will produce the phenomenon of sticking the kettle and winding the stirring paddle, which has a great influence on the normal operation of the reactor and the heat exchange of the materials in the reactor, which is not conducive to industrial continuous production. In addition, a large amount of cocatalyst fluorenyl aluminoxane is required in the homogeneous catalytic system, which increases the production cost of polyolefin, and also has an adverse effect on product performance due to the introduction of a large amount of cocatalyst, and some even need to be in the latter order. The removal of aluminum introduced during the polymerization during processing further increases the cost of the process. An olefin polymerization and copolymerization catalyst or catalytic system prepared by the patent W003/010207 has a wide range of olefin polymerization and copolymerization properties, and is suitable for various forms of polymerization processes, but requires a higher amount of cocatalyst in the polymerization of olefins. A suitable olefin polymerization activity is obtained, and there is a sticking phenomenon in the polymerization process. According to the experience of industrial application of metallocene olefin polymerization catalysts (Chem Rev, 2000, 100: 1347; Chem Rev, 2000, 100: 1377), loading of a homogeneous non-metallocene olefin polymerization catalyst is necessary.
催化剂负载化的主要目的是为了改善催化剂的聚合性能和聚合物 的成粒形态。 其表现为在一定程度上适当降低了催化剂的初始活性， 从而减少甚至避免了聚合过程中的结块或暴聚现象； 催化剂经负载化 后能够改善聚合物的形态， 提高聚合物的表观密度， 可以使其满足更 多的聚合工艺过程， 如气相聚合或淤浆聚合等， 同时负载化过程可以 大幅度地降低催化剂的制备和烯烃聚合成本， 改善聚合性能， 延长催 化剂聚合活性寿命等。 EP 0206794使用 MA0改性氧化物载体和随后使 用金属茂， 客观上限制了载体材料的性能对聚合物颗粒度的控制能 力。 EP 685494 将甲基铝氧烷作用于亲水性氧化物， 用多官能度有机 交联剂和随后使用活化 MA0 /金属茂配合物， 有可能降低聚合产物的 堆积密度， 不利于工业使用。  The main purpose of catalyst loading is to improve the polymerization properties of the catalyst and the granulation morphology of the polymer. It is characterized by appropriately reducing the initial activity of the catalyst to a certain extent, thereby reducing or even avoiding agglomeration or agglomeration in the polymerization process; the catalyst can improve the morphology of the polymer and increase the apparent density of the polymer after being supported. It can satisfy more polymerization processes, such as gas phase polymerization or slurry polymerization, and the loading process can greatly reduce catalyst preparation and olefin polymerization cost, improve polymerization performance, and prolong the polymerization activity life of the catalyst. EP 0206794 uses MA0 to modify the oxide support and subsequently the metallocene, which objectively limits the ability of the support material to control the particle size of the polymer. EP 685494 The action of methylaluminoxane on hydrophilic oxides, the use of polyfunctional organic crosslinkers and the subsequent use of activated MAO/metallocene complexes, has the potential to reduce the bulk density of the polymerized product, which is detrimental to industrial use.
专利 CN 1352654选用有机铝、 有机硅、 有机镁和有机硼化合物处 理载体， 然后负载杂原子配体的单中心烯烃聚合催化剂， 所得到的负 载型催化剂具有高活性和长贮存期。 EP 295312 描述了在有机或无机 粒状载体存在的情况下， 将铝氧浣溶液和一种不能溶解铝氧烷的溶剂 接触， 导致铝氧烷沉淀在载体上。 W0 97/26285 描述高压下制备负载 型茂金属催化剂的方法， 生产周期长， 负载效率不高。 而 CN 1307065 在超声波振荡作用下， 用烷基铝氧烷处理载体后负载茂金属催化剂， 负载化过程并不经济。  Patent CN 1352654 selects a single-center olefin polymerization catalyst which is treated with an organoaluminum, a silicone, an organomagnesium and an organoboron compound, and then carries a hetero atom ligand, and the resulting supported catalyst has high activity and long shelf life. EP 295 312 describes contacting an aluminoxane solution with a solvent which does not dissolve the aluminoxane in the presence of an organic or inorganic particulate carrier, resulting in precipitation of the aluminoxane on the support. W0 97/26285 describes a method for preparing a supported metallocene catalyst at high pressure with a long production cycle and low loading efficiency. However, CN 1307065 is supported by a metal aluminoxane after the carrier is treated with an alkyl aluminoxane, and the loading process is not economical.
为了提高载体和催化剂之间的结合强度， CN 1162601 采用双官能 度交联剂继续处理经过铝氧烷或烷基铝化合物处理的载体。 专利 CN 1174849将脱羟基的二氧化硅在甲苯介质中用 MA0处理后 ， 再负载茂 金属催化剂， 文中没有给出负载型催化剂的聚合活性数据。 专利 CN1120550 提出一种催化剂负载化的方法， 其主要是将亲水的、 大孔 的、 细碎的无机载体， 先热活化后与铝氧烷反应， 继而与多官能有机 交联剂反应， 最后与金属茂和活化剂的反应产物混合， 从而制得负载 型金属茂催化剂， 但在负载过程中铝氧烷的用量较高。 CN 1053673 采 用微波作用使催化剂和负载在载体材料上的助催化剂在悬浮液中互相 接触， 进而制得一种稳定结构的负载型催化剂， 但这种方法需要微波 装置， 操作起来并不简单。 CN1323319 采用催化剂材料浸渍机械流动 状态的多孔颗粒载体， 即将相当于载体孔体积的催化剂溶液喷至载体 上， 进而干燥制得负载型催化剂， 这种负载化方法客观上要求催化剂 的溶解度足够大， 否则不能保证催化剂负载的均匀性和负载量。 专利 WO96/ 00243 描述了一种负载型催化剂組合物的制备方法， 包括在溶剂 中混合桥连的双茚基金属茂和铝氧烷形成溶液， 然后使所述溶液与多 孔载体结合， 其中所述溶液的总体积低于形成浆液时的溶液体积。 In order to increase the bond strength between the support and the catalyst, CN 1162601 continues to treat the support treated with the aluminoxane or the alkylaluminum compound using a bifunctional crosslinking agent. Patent CN 1174849, after treating the dehydroxylated silica with MA0 in a toluene medium, and then supporting the metallocene catalyst, the polymerization activity data of the supported catalyst is not given herein. Patent CN1120550 proposes a catalyst loading method, which mainly comprises a hydrophilic, macroporous, finely divided inorganic carrier, which is first thermally activated and then reacted with an aluminoxane, and then reacted with a polyfunctional organic crosslinking agent, and finally The reaction product of the metallocene and the activator is mixed to produce a supported metallocene catalyst, but the amount of aluminoxane is higher during the loading process. CN 1053673 The use of microwaves to contact a catalyst and a cocatalyst supported on a support material in a suspension to produce a supported catalyst of stable structure, but this method requires microwave The device is not easy to operate. CN1323319 The catalyst material is used to impregnate a porous particle carrier in a mechanical flow state, that is, a catalyst solution corresponding to the pore volume of the carrier is sprayed onto the carrier, and then dried to obtain a supported catalyst. The loading method objectively requires that the solubility of the catalyst is sufficiently large, otherwise The uniformity and load of the catalyst load cannot be guaranteed. Patent WO 96/00243 describes a process for the preparation of a supported catalyst composition comprising mixing a bridged bis-indenyl metallocene and an aluminoxane in a solvent to form a solution, and then combining the solution with a porous support, wherein The total volume of the solution is lower than the volume of the solution when the slurry is formed.
以无水氯化镁为载体的催化剂在烯烃聚合过程中显示出较高的催 化活性， 但此类催化剂非常脆， 在聚合反应器中容易破碎， 从而导致 聚合物形态不好。 二氧化硅负载的催化剂具有很好的流动性， 可用于 气相流化床聚合， 但二氧化硅负载茂金属和非茂催化剂则表现出较低 的催化活性。 因此如果将氯化镁和二氧化硅进行很好的有机结合， 就 可能制备出具有高催化活性， 粒度大小可控及良好耐磨损强度的催化 剂。  Catalysts based on anhydrous magnesium chloride show higher catalytic activity during the polymerization of olefins, but such catalysts are very brittle and are easily broken in the polymerization reactor, resulting in poor polymer morphology. Silica-supported catalysts have good flow properties and can be used in gas phase fluidized bed polymerization, but silica supported metallocene and non-catalysts exhibit lower catalytic activity. Therefore, if magnesium chloride and silica are well combined, it is possible to prepare a catalyst having high catalytic activity, controlled particle size and good wear resistance.
EP 0878484 4艮道了用低氯化镁含量（小于 3 % ) 的 MgCl2/S i02双 载体负载锆茂金属制备的催化剂可用于乙烯的均聚或共聚， 具有较好 的催化活性。 EP 0878484 4 is a catalyst prepared by using a MgCl 2 /S i0 2 dual support supported zirconium metallocene with a low magnesium chloride content (less than 3%) for homopolymerization or copolymerization of ethylene, and has good catalytic activity.
专利 CN 1364817 公开了氯化镁 /二氧化硅负载的 β -二酮半茂钛 金属催化剂的制备方法和聚合应用， 其乙烯聚合活性达到 7. 42 x 10s 克聚乙烯 /摩尔钛 .小时， 但专利中没有关于聚合物成粒性能方面的 具体数据。 Patent CN 1364817 discloses a preparation method and a polymerization application of a magnesium chloride/silica supported β-diketone semi-titanium metal catalyst having an ethylene polymerization activity of 7.42 x 10 sg of polyethylene per mole of titanium. There is no specific data on the granulation properties of the polymer.
专利 EP260130提出将负载型茂金属或非茂过渡金属催化剂负载于 甲基铝氧烷处理的二氧化硅载体之上， 这里的非茂过渡金属仅仅是指 ZrCl4、 TiCl4或者 V0C13， 专利认为最优的是载体表面经有机镁或镆化 合物与烷基铝的混合物， 但是这个过程比较复杂， 需要经过许多制备 步骤。 Patent EP 260130 proposes to support a supported metallocene or non-auxiliary transition metal catalyst on a methylaluminoxane-treated silica support, where the non-roamed transition metal merely refers to ZrCl 4 , TiCl 4 or V0C1 3 , the patent Most preferably, the surface of the support is a mixture of organomagnesium or a ruthenium compound and an aluminum alkyl, but this process is complicated and requires many preparation steps.
专利 CN1539856A提出将非茂金属催化剂负载于二氧化硅和氯化镁 所形成的复合载体上， 并将由此得到的负载型非茂金属催化剂与甲基 铝氧烷组成聚合用催化剂体系， 用于烯烃聚合。  Patent CN1539856A proposes to support a non-metallocene catalyst on a composite support formed of silica and magnesium chloride, and the supported non-metallocene catalyst and methylaluminoxane thus obtained are used in a polymerization catalyst system for olefin polymerization.
专利 W003/ 047752A1 和 W003/047751A1 提供了复合催化剂 （齐格 勒-纳塔与茂金属催化剂、 或者非茂金属催化剂和茂金属催化剂） 在 二氧化硅上的负载化方法， 专利认为， 钛或钒的氯化物或氯氧化合物 是非茂金属催化剂组份， 由此得到的催化剂是双金属催化剂。 Patents W003/ 047752A1 and W003/047751A1 provide a method for loading a composite catalyst (Ziegler-Natta with a metallocene catalyst, or a non-metallocene catalyst and a metallocene catalyst) on silica, the patent claims that titanium or vanadium Chloride or oxychloride It is a non-metallocene catalyst component, and the catalyst thus obtained is a bimetallic catalyst.
烯烃聚合催化剂的活性是其应用的首要条件。 但是， 非茂金属催 化剂经过惰性载体负载后， 催化烯烃聚合活性都会有或多或少的减 少， 有些甚至活性降低一个数量级以上， 从而导致负载型催化剂在应 用上的不经济。 更为甚者， 活性降低后， 所得聚合物灰分增加， 在生 产中需要附加脱灰工艺， 更导致成本增加和生产装置的复杂度， 限制 了其在聚烯烃催化生产中的进一步应用。  The activity of the olefin polymerization catalyst is a primary condition for its application. However, when the non-metallocene catalyst is supported by an inert carrier, the catalytic olefin polymerization activity is more or less reduced, and some even reduce the activity by more than an order of magnitude, resulting in an uneconomical application of the supported catalyst. What is more, after the activity is reduced, the ash content of the obtained polymer is increased, and an additional deliming process is required in the production, which leads to an increase in cost and complexity of the production apparatus, and limits its further application in the catalytic production of polyolefin.
关于聚合工艺， 已知在工业化进程中， 基于不同催化剂的聚合反 应系统主要包括如下几种： 高压过程， 聚合压力大于 50MPa， 采用搅 拌釜或管式反应器。 Exxon 最先开发成功， 在 Baton Rouge 高压聚合 工厂用 Exxpol®单中心催化剂生产 Exact®, 产品性能介于弹性体和低 密度聚乙烯热塑料。 但高压过程对设备的要求很高， 固定资产投资巨 大。 溶液法， 比较适合均相单中心催化剂。 1993年 Dow使用 CGC催化 剂在 Taxas 利用 Ins i te®技术生产塑性体和弹性体， 随后在西班牙 Tarragona利用 Ins i te®技术生产弹性体、 塑性体和增强型 LLDPE, 即 Engage®0 1996年在 LA的工厂生产塑性体 Aff ini ty®和弹性体 Engage®。 Hoechs t、 Nova , Dex Plas tomers 和三井油化均开发了溶液法技术。 气相法， 是目前发展的趋势。 其简单、 低价、 宽产品分布， 尤其适合 共聚。 BASF、 UCC、 BP三井、 Montel K Boreal i s均开发了气相法技术。 其中以 UCC和 BP的流化床， 以及 Elenac的搅拌床反应器最为典型。 淤浆法， 适用范围较宽， 工业上最为典型的是 Phi l l ips和 Solvay的 连续环管反应过程， Elenac 的搅拌釜反应器、 Nissan, 三井的双釜 fe 拌反应器。 淤浆法无搅动粘度问题， 反应介盾均匀， 反应热容易排除； 聚合产率高， 可以生产很高重均分子量的聚合物， 以及回收聚合物的 能量节省和投资费、 生产成本低。 Regarding the polymerization process, it is known that in the industrialization process, the polymerization system based on different catalysts mainly includes the following: High pressure process, polymerization pressure greater than 50 MPa, using a stirred tank or a tubular reactor. Exxon was first developed and produced Exact® with Exxpol® single-site catalyst at the Baton Rouge high pressure polymerization plant, with properties ranging from elastomers to low density polyethylene thermoplastics. However, the high-pressure process has high requirements on equipment and the investment in fixed assets is huge. The solution method is more suitable for homogeneous single-site catalysts. In 1993 Dow used CGC catalysts to produce plastomers and elastomers at Taxas using Ins i te® technology, followed by Ins i te® technology in Tarragona, Spain to produce elastomers, plastomers and enhanced LLDPE, ie Engage® 0 in LA in 1996. The factory produces plastomers Aff inty® and elastomer Engage®. Solution technology was developed by Hoechs t, Nova, Dex Plas tomers and Mitsui Oil Chemical. The gas phase method is the current development trend. Its simple, low price, wide product distribution, especially suitable for copolymerization. BASF, UCC, BP Mitsui, and Montel K Boreal are all developed gas phase technology. Among them, the fluidized bed of UCC and BP, and the stirred bed reactor of Elenac are the most typical. The slurry method has a wide range of applications. The most typical in the industry is the continuous loop reaction process of Phi ll ips and Solvay, the stirred tank reactor of Elenac, the Nissan, and the three-cylinder fe-mix reactor of Mitsui. The slurry method has no agitation viscosity problem, the reaction medium is uniform, and the reaction heat is easily eliminated; the polymerization yield is high, the polymer having a very high weight average molecular weight can be produced, and the energy saving and investment cost and production cost of the recovered polymer are low.
W09729138 公开了在流化床反应器中， 可以用降低乙烯分压和采 用不 聚合温度来提高乙烯均聚过程，最优的结果是乙烯采用 60 ~ 120 Ps i 的分压， 反应温度 90 ~ 120 ， 专利发现这个乙烯均聚过程与负 载型茂金属的种类无关。  W09729138 discloses that in a fluidized bed reactor, it is possible to increase the ethylene partial pressure by lowering the partial pressure of ethylene and using a non-polymerization temperature. The best result is that ethylene has a partial pressure of 60 to 120 Ps i and a reaction temperature of 90 to 120. The patent found that this ethylene homopolymerization process is independent of the type of supported metallocene.
在选择催化剂的聚合工艺时， 需要考虑聚合工艺对催化剂的适应 性、 投资成本、 以及装置运行复杂程度和成本， 同时还要参考聚合工 艺对聚合产品的性能调节和控制， 以及改变聚合条件与产品性能之间 对应关系。 高压法工艺和溶液法工艺比较适合非负载的茂金属催化剂 或非茂金属催化剂， 而气相法工艺和淤浆法工艺最为适合负载的茂金 属催化剂或非茂金属催化剂。 In selecting the polymerization process of the catalyst, it is necessary to consider the adaptability of the polymerization process to the catalyst, the investment cost, and the complexity and cost of the operation of the device, and also refer to the performance adjustment and control of the polymerization product by referring to the polymerization process, and changing the polymerization conditions and products. Between performance Correspondence relationship. The high pressure process and the solution process are suitable for unsupported metallocene catalysts or non-metallocene catalysts, while the gas phase process and the slurry process are most suitable for supported metallocene catalysts or non-metallocene catalysts.
对于负载型新型的非茂金属催化剂的工业应用， 首先需要考虑两 者之间的相容难易程度。 最优的方式是仅通过对现有工艺的少量调整 就可以实现这种负载型非茂金属催化剂在现有工业装置的应用。 专利 For the industrial application of a new type of supported non-metallocene catalyst, it is first necessary to consider the degree of compatibility between the two. The most advantageous way is to achieve the application of such supported non-metallocene catalysts in existing industrial plants by only minor adjustments to existing processes. patent
US5352749 介绍 mPE 需对现有工艺的改进情况， 首先是单体的精制过 程， 催化剂贮存、 配制、 处理及反应器进料工序； 严格氢调系统； 挤 出系统改进。 发明筒述 US 5,352,749 describes the improvement of existing processes for mPE, starting with the monomer refining process, catalyst storage, formulation, treatment and reactor feed operations; stringent hydrogen regulation systems; and extrusion system improvements. Invention
为此， 本发明的一个目的是在现有技术的基础上提供一种负载型 非茂金属烯烃聚合催化剂的负载化方法。 具体而言， 本发明涉及一种 非茂金属烯烃聚合催化剂在载体上的负载化方法。  To this end, it is an object of the present invention to provide a supported method of a supported non-metallocene olefin polymerization catalyst based on the prior art. In particular, the present invention relates to a method of loading a non-metallocene olefin polymerization catalyst on a support.
本发明的载体负载型非茂金属烯烃聚合催化剂的负载化方法包括 以下步骤：  The supported method of the support-supported non-metallocene olefin polymerization catalyst of the present invention comprises the following steps:
使载体与化学活化剂作用， 得到修饰载体；  The carrier is allowed to react with a chemical activator to obtain a modified carrier;
将镁化合物溶解于四氢呋喃 -醇混合溶剂中形成溶液， 再将所述 修饰载体加入到此溶液中进行反应， 经过滤洗涤、 干燥和抽干后， 制 得复合载体；  The magnesium compound is dissolved in a tetrahydrofuran-alcohol mixed solvent to form a solution, and the modified carrier is added to the solution to carry out a reaction, followed by filtration washing, drying and drying to obtain a composite carrier;
将非茂金属烯烃聚合催化剂溶解于溶剂中， 然后与所述复合载体 反应， 接着洗涤过滤、 干燥和抽干， 制得负载型非茂金属浠烃聚合催 化剂。  The non-metallocene olefin polymerization catalyst is dissolved in a solvent, then reacted with the composite support, followed by washing, filtration, drying and drying to obtain a supported non-metallocene terpene hydrocarbon polymerization catalyst.
以上方法的优化方案是， 增加以下步骤中的一个或两个： 所述载体在与所述化学活化剂作用之前， 进行过热活化处理； 所述复合载体在与所述非茂金属烯烃聚合催化剂反应之前， 先与 化学处理剂作用， 制得修饰复合载体， 然后再使所述修饰复合载体与 所述非茂金属烯烃聚合催化剂反应， 从而制得所述负载型非茂金属烯 烃聚合催化剂。  An optimization of the above method is to add one or both of the following steps: the carrier is subjected to a superheat activation treatment before the action with the chemical activating agent; the composite carrier is reacted with the non-metallocene olefin polymerization catalyst Previously, a modified composite support is prepared by reacting with a chemical treatment agent, and then the modified composite support is reacted with the non-metallocene olefin polymerization catalyst to prepare the supported non-metallocene olefin polymerization catalyst.
本发明所涉及的非茂金属烯烃聚合催化剂是具有如下结构的配合 物： -IVIXn
Figure imgf000008_0001
其中： The non-metallocene olefin polymerization catalyst according to the present invention is a complex having the following structure: -IVIXn
Figure imgf000008_0001
among them:
m代表 1、 2或 ^  m stands for 1, 2 or ^
q代表 0或 I;  q stands for 0 or I;
d代表 0或 1;  d represents 0 or 1;
n代表 1、 2、 3或 4;  n stands for 1, 2, 3 or 4;
M代表过渡金属原子；  M represents a transition metal atom;
X是选自卤原子、 氢原子、 C3。的烃基及 C3。的取代的烃基、 含氧基团、 含氮基团、 含硫基团、 含硼基团、 含铝基团、 含磷基团、 含硅基团、 含锗基团、 或含锡基团的基团， 几个配体 X可以相同， 也 可以不同， 还可以彼此成键或成环； X is selected from a halogen atom, a hydrogen atom, and C 3 . Hydrocarbyl group and C 3 . Substituted hydrocarbyl group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, ruthenium-containing group, or tin-containing group a group, several ligands X may be the same or different, and may also be bonded or looped to each other;
其中， 结构式中所有配体所带负电荷总数的绝对值应与结构式中 金属 M所带正电荷的绝对值相同， 所有配体包括配体 X及多齿配体，
Figure imgf000008_0002
Wherein, the absolute value of the total negative charge of all ligands in the structural formula should be the same as the absolute value of the positive charge of the metal M in the structural formula, and all ligands include ligand X and multidentate ligands,
Figure imgf000008_0002
R1 。 3)q R 1 . 3 )q
其中该多齿配体指的是结构式中的 R ； Wherein the polydentate ligand refers to R in the structural formula;
A代表氧原子、 硫原子、 硒原子、 R21N或 R21P; A represents an oxygen atom, a sulfur atom, a selenium atom, R 21 N or R 21 P;
B表含氮基团、 含磷基团或 Ci - C3。的烃类； Table B contains a nitrogen group, a phosphorus containing group or Ci - C 3 . Hydrocarbons;
D代表氧原子、 硫原子、 硒原子、 含（^ - C3。烃基的含氮基团、 含 (^ - C3。的烃基的含氮或含 - ( 3。的烃基的含磷基团， 其中 N、 0、 S、 Se、 P为配位原子； D represents an oxygen atom, a sulfur atom, a selenium atom, an (^ - C 3 hydrocarbon group is a nitrogen-containing group, containing (^ - a nitrogen-containing hydrocarbon group or a C 3 containing -. (3 phosphorus-containing hydrocarbyl group Wherein N, 0, S, Se, P are coordinating atoms;
E 代表含氮基团、 含氧基团、 含硫基团、 含硒基团或含磷基团， 其中 N、 0、 S、 Se、 P为配位原子；  E represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordinating atoms;
代表单键或双键；  Represents a single or double button;
代表配位键、 共价键或离子键; 一代表共价键或离子键；Representing a coordination bond, a covalent bond or an ionic bond; One represents a covalent bond or an ionic bond;
Figure imgf000009_0001
的取代 烃基或 功能性基团， II1、 R2、 R3、 R21基团彼此间可以相同也可以 不同， 其中相邻基团如 R R2 , R3部分可以彼此成键或成环；
Figure imgf000009_0001
a substituted hydrocarbyl group or a functional group, the II 1 , R 2 , R 3 , R 21 groups may be the same or different from each other, wherein adjacent groups such as RR 2 , R 3 moieties may be bonded or ringed to each other;
本文中， 烃基指含 C3。的烷基、 （：广^。的环状烃基、 C2- C3()的含 碳碳双键的基团、 C2-C3。的含碳碳三键的基团、 C6- C3。的芳香烃基、 C8- c30的稠环烃基或 c4- c3。的杂环基。 Herein, the hydrocarbon group means C 3 . An alkyl group, a cyclic hydrocarbon group, a carbon-carbon double bond group of C 2 - C 3 () , a C 2 -C 3 carbon-carbon triple bond group, C 6 - a C 3 aromatic hydrocarbon group, a C 8 - c 30 fused ring hydrocarbon group or a c 4 - c 3 heterocyclic group.
该催化剂优选具有下列结构的非茂金属催化剂：  The catalyst is preferably a non-metallocene catalyst having the following structure:
Figure imgf000009_0002
Figure imgf000009_0002
以上所述的非茂金属烯烃聚合催化剂进一步为具有如下结构的配 合物:  The above non-metallocene olefin polymerization catalyst is further a compound having the following structure:
Figure imgf000009_0003
Figure imgf000009_0003
其主要包括下述结构的催化剂 IVA和 IVB:  It mainly includes catalysts IVA and IVB of the following structure:
Figure imgf000009_0004
(IVA) (IVB)。 为了更清楚地理解催化剂 IVA， 我们可以用 IVA - IVA - 2， IVA - 3和 IVA- 4来细化描述。
Figure imgf000009_0004
(IVA) (IVB). In order to understand the catalyst IVA more clearly, we can use IVA - IVA - 2, IVA - 3 and IVA-4 to refine the description.
Figure imgf000010_0001
Figure imgf000010_0001
IVA - 3 IVA-4  IVA - 3 IVA-4
为了更清楚地理解催化剂 IVB， 我们可以用 IVB- 1， IVB - 2, IVB - 3和 IVB- 4来细化描述。  For a clearer understanding of the catalyst IVB, we can use IVB-1, IVB-2, IVB-3 and IVB-4 to refine the description.
Figure imgf000010_0002
在上述的所有结构中：
Figure imgf000010_0002
In all the above structures:
m代表 1、 2或 3  m stands for 1, 2 or 3
q代表 0或 1;  q stands for 0 or 1;
d代表 0或 1;  d represents 0 or 1;
M代表过渡金属原子， 尤其是钛、 锆、 铪、 铬、 铁、 钴、 镍或钯； N代表 1、 2、 3或 4;  M represents a transition metal atom, especially titanium, zirconium, hafnium, chromium, iron, cobalt, nickel or palladium; N represents 1, 2, 3 or 4;
X是选自卤原子、 氢原子、 CI - C30的烃基及 C1 -C30的取代的烃 基、 含氧基团、 含氮基团、 含硫基团、 含硼基团、 含铝基团、 含磷基 团、 含硅基团、 含锗基团、 或含 基团的基团， 其中结构式中几个配 体 X可以相同， 也可以不同， 还可以彼此成键或成环；  X is a halogen atom, a hydrogen atom, a hydrocarbon group of CI - C30, a substituted hydrocarbon group of C1 - C30, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus group, a silicon-containing group, a hydrazine-containing group, or a group containing a group, wherein several ligands X in the structural formula may be the same or different, and may also be bonded or ring-bonded to each other;
这里的卤原子包括氟、 氯、 溴或碘；  The halogen atom herein includes fluorine, chlorine, bromine or iodine;
结构式中所有配体所带负电荷总数的绝对值应与结构式中金属 M 所带正电荷的绝对值相同， 所有配体包括配体 X及多齿配体， 其中该  The absolute value of the total negative charge of all ligands in the structural formula shall be the same as the absolute value of the positive charge of the metal M in the structural formula, and all ligands include ligand X and polydentate ligand, wherein
多齿配体指的是结构式中的
Figure imgf000011_0001
；Multidentate ligand refers to the structural formula
Figure imgf000011_0001
;
NR22 NR 22
A代表氧原子、 硫原子、 硒原子、 I 、 一 NR23R24、 一 N(0)R25R26、
Figure imgf000011_0002
、 一 PR28R29、 一 P(0)R3。R31、 砜基、 亚砜基或一 Se(0)R39; A represents an oxygen atom, a sulfur atom, a selenium atom, I, a NR 23 R 24 , an N(0)R 25 R 26 ,
Figure imgf000011_0002
, a PR 28 R 29 , a P (0) R 3 . R 31 , sulfone group, sulfoxide group or a Se(0)R 39 ;
B代表指含氮基团、 含磷基团或 C3。的烃类； B represents a nitrogen-containing group, a phosphorus-containing group or C 3 . Hydrocarbons;
D代表氧原子、 硫原子、 硒原子、 含（^-(3。烃基的含氮基团、 舍
Figure imgf000011_0003
烃基的含碑基团、 砜基、 亚砜基、 - P(0)R3°R31或一 P(0)R32(OR33) , 其中 N、 0、 S、 Se、 P为配位原子; D represents an oxygen atom, a sulfur atom, a selenium atom, and contains (^-( 3 . a hydrocarbon group-containing nitrogen group,
Figure imgf000011_0003
a hydrocarbon group containing a group, a sulfone group, a sulfoxide group, -P(0)R 3 °R 31 or a P(0)R 32 (OR 33 ), wherein N, 0, S, Se, P are coordination atom;
E 代表含氮基团、 含氧基团、 含硫基团、 含硒基团或含磷基团， 其中 N、 0、 S、 Se、 P为配位原子；  E represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordinating atoms;
F 代表含氮基团、 含氧基团、 含硫基团、 含 基团或含磷基团， 其中 N、 0、 S、 Se、 P为配位原子；  F represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a group-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordination atoms;
G代表惰性基团或惰性功能性基团， 包括 - C3。烃基、 - C3。的 取代的烃基或惰性功能性基团； G represents an inert group or an inert functional group, including -C 3 . Hydrocarbyl group, -C 3 . Substituted hydrocarbyl or inert functional group;
Y, z代表含氮基团、 含氧基团、 含硫基团、 含 基固或含磷基团， N、 0、 S、 Se、 P为配位原子； Y, z represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a solid-containing or phosphorus-containing group, N, 0, S, Se, P are coordination atoms;
—代表单键或默键；  - represents a single key or a silent key;
......代表配位键、 共价键或离子键；  ... represents a coordination bond, a covalent bond or an ionic bond;
一代表共价键或离子键；  One represents a covalent bond or an ionic bond;
R R2、 R3、 R4、 R5、 R10、 Ru、 R12、 R13、 R14、 R15、 Rlfi、 R17、 R18、 R13、RR 2 , R 3 , R 4 , R 5 , R 10 , R u , R 12 , R 13 , R 14 , R 15 , R lfi , R 17 , R 18 , R 13 ,
R20 R21 R22 R23 R24 R27 R28 R29 R30 R31 R32 R33 R34 R35 R36 R38、 R39选自氢、 C3。烃基、 卤素原子、 （^-03。的取代烃基（特别是 指卤代的烃基， 如一 CH2C1 或一 CH2CH2C1 )或惰性功能基团， 上述基团 彼此间可以相同也可以不同， 其中相邻基团如 R1与 R2， R3、 R3与 R4、 R6 R7、 R8、 R9以及 R23与 R24 或 R25与 R2S等可以彼此成键或成环； R 20 R 21 R 22 R 23 R 24 R 27 R 28 R 29 R 30 R 31 R 32 R 33 R 34 R 35 R 36 R 38 and R 39 are selected from the group consisting of hydrogen and C 3 . a hydrocarbon group, a halogen atom, a substituted hydrocarbon group of (^-0 3 (particularly a halogenated hydrocarbon group such as a CH 2 C1 or a CH 2 CH 2 C1 ) or an inert functional group, the above groups may be the same as each other Different, wherein adjacent groups such as R 1 and R 2 , R 3 , R 3 and R 4 , R 6 R 7 , R 8 , R 9 and R 23 and R 24 or R 25 and R 2S may be bonded to each other Or into a ring;
R5代表氮上孤对电子、 氢、 （^- C3。烃基、 （^-C 的取代的烃基、 含氧基团， 包括羟基， 烷氧基 - OR34， 带有醚基的烷基， 包括一 T- OR34、 含硫基团， 包括- SR35、 -T-SR35, 含氮基团， 包括 -NR23R24、 -T- NR23R24， 含磷基团， 包括一 PR28R29、 - T-PR2SR29、 — T— P (0) R3°R31; 当 R5为含氧基团、 含硫基团、 含氮基团、 含 基团或含磷基团时， R5中 的1(、 0、 S、 P、 Se也可以参与金属的配位； R 5 represents a lone pair of electrons on the nitrogen, hydrogen, (^-C 3 . a hydrocarbyl group, a substituted hydrocarbyl group of ^-C, an oxygen-containing group, including a hydroxyl group, an alkoxy group - OR 34 , an alkyl group having an ether group , comprising a T-OR 34 , a sulfur-containing group, including -SR 35 , -T-SR 35 , a nitrogen-containing group, including -NR 23 R 24 , -T-NR 23 R 24 , a phosphorus-containing group, including a PR 28 R 29 , - T-PR 2S R 29 , — T— P (0) R 3 °R 31 ; when R 5 is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a group-containing group or In the case of a phosphorus-containing group, 1 (, 0, S, P, Se in R 5 may also participate in the coordination of the metal;
T代表 Ci- C3。烃基、 C3Q的取代烃基或惰性功能性基团。 T stands for Ci-C 3 . a hydrocarbyl group, a substituted hydrocarbyl group of C 3Q or an inert functional group.
该非茂金属烯烃聚合催化剂比如可以举出下列的非茂金属烯烃聚 合催化剂：  The non-metallocene olefin polymerization catalyst may, for example, be exemplified by the following non-metallocene olefin polymerization catalyst:
Figure imgf000012_0001
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0002
Figure imgf000013_0003
Figure imgf000013_0003
Figure imgf000013_0004
Figure imgf000013_0004
Figure imgf000013_0005
Figure imgf000013_0005
- 11 - - 11 -
Figure imgf000014_0001
Figure imgf000014_0001
其中， 优选结构为如下所示的非茂金属烯烃聚合催化剂 Among them, a preferred structure is a non-metallocene olefin polymerization catalyst as shown below
Figure imgf000014_0002
最优选的是结构如下所示的非茂金属烯烃聚合催化剂:
Figure imgf000014_0002
Most preferred are non-metallocene olefin polymerization catalysts having the structure shown below:
Figure imgf000014_0003
Figure imgf000014_0003
在本发明中， 元素和金属隶属于某一族均是指按该元素周期表的 族和族群对应于用 IUPAC体系编組的族或族群作为依据的。  In the present invention, the fact that the element and the metal belong to a certain family means that the family and the group according to the periodic table of the elements correspond to the group or group grouped by the IUPAC system.
本发明所用的多孔固体可以是任意的、 表面具有官能团的多孔固 体。 其可以是： 含有有机官能团的有机材料如聚乙烯、 聚丙烯、 聚丁 烯、 聚乙烯醇、 环糊精和上述聚合物所基于的单体的共聚物， 聚酯、 聚酰胺、 聚氯乙烯、 聚丙烯酸酯、 聚曱基丙烯酸酯、 聚苯乙烯、 或部 分交联的聚合物， 而有机官能团选自羟基、 伯 基、 仲氨基、 磺酸基、 羧基、 酰胺基、 N -单取代的酰胺基、 磺酸胺基、 N-单取代的横酸胺 基、 巯基、 酰亚氨基和酰肼基。 优选部分交联、 具有表面羟基官能团 的苯乙烯聚合物， 还优选表面带有羧基的聚苯乙烯； 选自 Π Α、 ΙΠΑ、 IVA族和 IVB 族金属氧化物的固体无机氧化物或这些金属的卤化物， 如二氧化硅（又称为硅胶） 、 氧化铝、 氧化镁、 氧化钛、 氧化锆、 氧 化钍、 氯化镁， 以及这些无机氧化物所组成的混合物和混合氧化物， 其官能团选自表面羟基或羧基； 或是由气态金属氧化物或硅化合物通 过高温水解过程而制备的氧化材料； 或者粘土、 分子筛、 云母、 蒙脱 土、 膨润土、 硅藻土、 ZSM- 5 或 MCM- 41。 比较适宜作为本发明载体的 为表面具有羟基基团的， 包括二氧化硅， 以及二氧化硅与一种或多种 Π Α、 ΙΠΑ族金属的混合氧化物， 如二氧化硅-氧化镁混合氧化物、 二 氧化硅-氧化铝混合氧化物， 优选以二氧化硅、 氧化铝以及二氧化硅 与一种或多种 Π Α、 ΠΙΑ族金属氧化物的混合氧化物作为载体材料， 特 别优选二氧化硅作为载体（适宜的二氧化硅载体是任意的可购买的商 业产品， 如， Grace 955 , Grace 948 , Grace SP9-351 , Grace SP9-485 , Grace SP9-10046, Davs ion Syloid 245, ES70, ES70X, ES70Y, ES757 , Aeros il812 , 或 CS-2133 和 MS-3040 ) ， 二氧化硅在用于载体之前， 优选在 100- 1000 、 惰性气氛或减压条件下， 干燥或焙烧 l ~ 24h 进 行过热活化。 The porous solid used in the present invention may be any porous solid having a functional group on its surface. It may be: a copolymer of an organic material containing an organic functional group such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and a monomer on which the above polymer is based, polyester, polyamide, polyvinyl chloride , polyacrylate, polydecyl acrylate, polystyrene, or partially crosslinked polymer, and the organic functional group is selected from the group consisting of hydroxyl, primary, secondary, sulfonic, carboxy, amide, N-monosubstituted Amido, sulfonate amine, N-monosubstituted phosphonic acid, sulfhydryl, imido and hydrazide groups. Preferably partially crosslinked, having surface hydroxyl functional groups a styrene polymer, preferably also a polystyrene having a carboxyl group on the surface; a solid inorganic oxide selected from the group consisting of ruthenium, osmium, IVA and IVB metal oxides or a halide of these metals, such as silica (also Known as silica gel), alumina, magnesia, titania, zirconia, cerium oxide, magnesium chloride, and mixtures and mixed oxides of these inorganic oxides, the functional groups of which are selected from surface hydroxyl or carboxyl groups; or by gaseous metals An oxidizing material prepared by a high temperature hydrolysis process of an oxide or a silicon compound; or clay, molecular sieve, mica, montmorillonite, bentonite, diatomaceous earth, ZSM-5 or MCM-41. More suitable as the carrier of the present invention is a surface having a hydroxyl group, including silicon dioxide, and a mixed oxide of silicon dioxide and one or more anthracene or lanthanum metal, such as silica-magnesia mixed oxidation. a silica-alumina mixed oxide, preferably a silica, alumina and a mixed oxide of silicon dioxide and one or more lanthanum and lanthanum metal oxides as a support material, particularly preferably oxidizing Silicon is used as a carrier (suitable silica carrier is any commercially available product such as Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davs ion Syloid 245, ES70, ES70X , ES70Y, ES757, Aeros il812, or CS-2133 and MS-3040), the silica is dried or calcined for 1 to 24 hours for heat activation before being used in the carrier, preferably under 100-1000, inert atmosphere or reduced pressure. .
适合本发明需要的载体的表面积（BET法测定）优选 10 - 1000m2/g， 更优选为 100 600m2/g。 载体孔体积 （氮吸附法测定）优选 0. 1 ~ 4cm3/g, 更优选 0. 2 ~ 2cm3/g。 载体的平均粒径 （激光粒度仪测定）优 选 1 ~ 500μιη, 更优选 1 ~ 100μιη。 在上述的载体材料中， 优选选自 Π Α、 ΙΠΑ、 IVA族和 IVB 族金属氧化物的具有表面羟基的固体无机氧化物或 卤化物载体， 最优选二氧化硅。 其可以是任意形态的， 如粒状、 球状、 聚集体或其它形式。 羟基的含量可用已知的技术来测定， 如红外光讲 法、 核磁共振法、 四氯化钛法、 烷基金属或金属氢化物滴定技术。 The surface area (determined by the BET method) of the carrier suitable for the present invention is preferably from 10 to 1000 m 2 /g, more preferably from 100 to 600 m 2 /g. 2〜 2厘米3 /g。 The carrier pore volume (measured by the nitrogen adsorption method) is preferably 0. 1 ~ 4cm 3 / g, more preferably 0. 2 ~ 2cm 3 / g. The average particle diameter of the carrier (measured by a laser particle size analyzer) is preferably from 1 to 500 μm, more preferably from 1 to 100 μm. Among the above-mentioned support materials, a solid inorganic oxide or halide carrier having a surface hydroxyl group selected from the group consisting of ruthenium, osmium, group IVA and group IVB metal oxides is preferred, and silica is most preferred. It may be in any form, such as granules, spheres, aggregates or other forms. The hydroxyl group content can be determined by known techniques such as infrared light, nuclear magnetic resonance, titanium tetrachloride, metal alkyl or metal hydride titration techniques.
这里的化学活化剂， 可以比如是金属 化物、 金属烷基化物、 金 属烷氧基化物或它们的混合物， 具体而言， 比如是 ΙΠΑ、 IVB 或 VB族 金属的 1¾化物、 烷基化合物或 1¾代烷基化合物， 或者金属烷氧基化 物， 优选 fflA、 IVB或 VB族金属的卤化物、 烷基铝或铝氧烷等。  The chemical activator herein may be, for example, a metallization, a metal alkylate, a metal alkoxide or a mixture thereof, specifically, for example, a ruthenium, an IVB or a VB group metal compound, an alkyl compound or a 13⁄4 generation. The alkyl compound, or a metal alkoxide, is preferably a halide of a metal of the FFA, IVB or VB group, an aluminum alkyl or an aluminoxane or the like.
ΙΠΑ、 IVB 或 VB 族金属的卤化物， 比如可举出三氯化铝、 三溴化 铝、 三碘化铝、 四氯化钛、 四溴化钛、 四礁化钛、 四氯化锆、 四溴化 锆、 四碘化锆、 四氯化铪、 四溴化铪、 四碘化铪、 氯化钒、 溴化钒、 破化钒等。 优选四氯化钛、 三氯化铝、 四氯化籍、 氯化钒， 最优选四 氯化钛和三氯化铝。 The halide of the cerium, IVB or VB group metal, for example, aluminum trichloride, aluminum tribromide, aluminum triiodide, titanium tetrachloride, titanium tetrabromide, titanium tetrahydrate, zirconium tetrachloride, Zirconium tetrabromide, zirconium tetraiodide, antimony tetrachloride, antimony tetrabromide, antimony tetraiodide, vanadium chloride, vanadium bromide, Decompose vanadium and so on. Preferred are titanium tetrachloride, aluminum trichloride, tetrachloride, vanadium chloride, and most preferred are titanium tetrachloride and aluminum trichloride.
垸基铝比如可举出甲基铝、 乙基铝、 丙基铝、 异丁基铝或丁基铝 等。 优选乙基铝和异丁基铝， 最优选乙基铝；  Examples of the bismuth-based aluminum include methyl aluminum, ethyl aluminum, propyl aluminum, isobutyl aluminum or butyl aluminum. Preferred are ethyl aluminum and isobutyl aluminum, most preferably ethyl aluminum;
卤代烷基化合物比如可举出一,氯曱基铝、 二氯曱基铝、 一氯乙基 铝、 二氯乙基铝、 一氯丙基铝、 二氯丙基铝、 一氯异丁基铝、 二氯异 丁基铝、 一氯丁基铝、 二氯丁基铝等。 优选一氯乙基铝、 二氯乙基铝、 一氯异丁基铝和二氯异丁基铝， 最优选一氯乙基铝和二氯乙基铝。  Examples of the halogenated alkyl compound include chloromercaptoaluminum, dichloroindenyl aluminum, monochloroethylaluminum, dichloroethylaluminum, monochloropropylaluminum, dichloropropylaluminum, and monochloroisobutylaluminum. , dichloroisobutyl aluminum, monochlorobutyl aluminum, dichlorobutyl aluminum, and the like. Preferred are monochloroethylaluminum, dichloroethylaluminum, monochloroisobutylaluminum and dichloroisobutylaluminum, most preferably monochloroethylaluminum and dichloroethylaluminum.
铝氧烷可以采用线性型 （ I ) ：
Figure imgf000016_0001
The aluminoxane can be linear (I):
Figure imgf000016_0001
也就是 R2— (Al (R) -0) n - A1R2， That is, R 2 — (Al (R) -0) n - A1R 2 ,
和 /或环状型铝氧烷（ Π ) 的铝氧烷：
Figure imgf000016_0002
And/or cyclic aluminoxane ( Π ) aluminoxane:
Figure imgf000016_0002
也就是—（Al (R)—0— ) π + 2。 That is, - (Al (R) - 0 - ) π + 2 .
在结构 （ I ) 和 （ Π ) 中， R基团可以相同或不同， 且为 C1-C8 烷基， 所述铝氧烷包括曱基铝氧烷、 乙基铝氧烷、 异丁基铝氧烷或丁 基铝氧烷等。 在以上结构式中， 优选 R基团是相同的且为甲基、 乙基 或异丁基， 最优选曱基， η 为 1-50 的整数， 优选 10 ~ 30。 以上结构 式所代表的铝氧烷比如优选曱基铝氧烷（MA0 ) 、 乙基铝氧烷（EA0 )、 异丁基铝氧烷（IBA0 ) 等。  In structures (I) and (Π), the R groups may be the same or different and are C1-C8 alkyl groups, and the aluminoxanes include mercaptoaluminoxane, ethylaluminoxane, isobutylaluminum oxide Alkane or butyl aluminoxane, and the like. In the above formula, it is preferred that the R groups are the same and are a methyl group, an ethyl group or an isobutyl group, most preferably a fluorenyl group, and η is an integer of from 1 to 50, preferably from 10 to 30. The aluminoxane represented by the above structural formula is preferably, for example, mercaptoaluminoxane (MA0), ethylaluminoxane (EA0), isobutylaluminoxane (IBA0) or the like.
更具体而言， 铝氧烷选自比如甲基铝氧垸、 乙基铝氧烷、 丙基铝 氧烷、 异丁基铝氧烷、 丁基铝氧烷或改性的曱基铝氧烷。 其中， 优逸 曱基铝氧烷、 乙基铝氧烷、 异丁基铝氧烷或改性的甲基铝氧烷， 最优 选甲基铝氧烷。  More specifically, the aluminoxane is selected, for example, from methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane or modified decyl aluminoxane. . Among them, Eudraphanyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane or modified methyl aluminoxane, most preferably methyl aluminoxane.
化学活化剂与载体的反应可采用任何方法进行， 只要能使载体与 化学活化剂实现接触从而使其发生反应即可。 比如可举出以下方法。  The reaction of the chemical activator with the carrier can be carried out by any method as long as the carrier can be brought into contact with the chemical activator to cause it to react. For example, the following methods can be mentioned.
将溶剂加入到载体中， 在溶剂的沸点以下进行搅拌， 再加入化学 活化剂或化学活化剂溶液， 如杲采用的液态的化学活化剂可直接加 入， 如果采用的是固态化学活化剂， 应首先将固态的化学活化剂溶解 于此溶剂中然后加入。 加入方式为滴加。 反应 0.5~24 小时后过滤， 并采用相同的溶剂进行洗涤 1 ~ 8次后干燥。 Adding the solvent to the carrier, stirring below the boiling point of the solvent, and adding a chemical activator or a chemical activator solution, such as a liquid chemical activator used in hydrazine, can be directly added. If a solid chemical activator is used, it should first Dissolve solid chemical activator This solvent is then added. The method of addition is dripping. The reaction was filtered for 0.5 to 24 hours, and washed with the same solvent for 1 to 8 times and then dried.
这里所述的溶剂也是任意的， 只要可以溶解化学活化剂， 或与化 学活化剂互溶即可， 比如选自 C5~C12 的液态碳氢化合物、 芳香化合 物或面代碳氢化合物， 如戊烷、 己烷、 庚烷、 辛烷、 壬烷、 癸烷、 十 一烷、 十二烷、 环己烷、 甲苯、 乙苯、 二曱苯、 氯代戊烷、 氯代己烷、 氯代庚烷、 氯代辛烷、 氯代壬垸、 氯代癸烷、 氯代十一烷、 氯代十二 烷、 氯代环己烷、 氯代曱苯、 氯代乙苯、 氯代二甲苯等， 优选戊烷、 己烷、 癸烷、 环己烷、 甲苯， 最优选己烷和甲苯。  The solvent described herein is also arbitrary as long as it can dissolve the chemical activator or be miscible with the chemical activator, such as a liquid hydrocarbon selected from C5 to C12, an aromatic compound or a surface hydrocarbon such as pentane. Hexane, heptane, octane, decane, decane, undecane, dodecane, cyclohexane, toluene, ethylbenzene, dinonylbenzene, chloropentane, chlorohexane, chloroheptane , chlorooctane, chlorohydrazine, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, chlorinated benzene, chloroethylbenzene, chloroxylene, etc. Pentane, hexane, decane, cyclohexane, toluene are preferred, and hexane and toluene are most preferred.
虽然选用较高的反应温度有助于化学活化剂与载体的反应， 可以 减少反应时间。 但是由于溶剂不同， 其沸点也是不同的。 本领域技术 人员都知道， 化学活化剂与载体的反应温度应低于溶剂的沸点， 比如 对于己烷而言， 反应温度可选择在 20Ό ~65Ό之间， 对于曱苯可选择 在 20°C ~105°C之间， 等等。 因此， 反应温度随溶剂的不同而不同， 不能一概而论， 但一般选择在低于溶剂沸点 5~ 101C之间， 反应时间 没有特别的限制， 一般可以选用 0.5-4 小时。 在提高反应温度的情 况下， 反应时间可以适当越短。  Although the use of a higher reaction temperature contributes to the reaction of the chemical activator with the support, the reaction time can be reduced. However, the boiling point is different due to the difference in solvent. It is known to those skilled in the art that the reaction temperature of the chemical activator and the carrier should be lower than the boiling point of the solvent. For example, for hexane, the reaction temperature can be selected between 20 Ό and 65 ,, and for benzene, the temperature can be selected at 20 ° C. Between 105 ° C, and so on. Therefore, the reaction temperature varies depending on the solvent, and it cannot be generalized, but it is generally selected to be between 5 and 101 C below the boiling point of the solvent, and the reaction time is not particularly limited, and generally 0.5 to 4 hours can be selected. In the case where the reaction temperature is raised, the reaction time can be appropriately shortened.
需要指出的是， 溶剂的使用并不是必需的。 化学活化剂与载体的 反应可以在没有溶剂存在的情况下进行。 此时化学活化剂必须为液 态， 但反应温度和反应时间可以根据需要适当确定， 但一般反应温度 应至少低于化学活化剂的沸点 5~10"Ό， 时间为 2~24 小时。 化学活 化剂与载体反应越激烈， 反应温度应该越低， 时间就越长。 比如化学 活化剂为四氯化钛时， 反应温度可以是- 30Ό ~126Ό之间进行， 对应 时间为 12 ~ 2小时。  It should be noted that the use of solvents is not required. The reaction of the chemical activator with the support can be carried out in the absence of a solvent. At this time, the chemical activator must be in a liquid state, but the reaction temperature and reaction time can be appropriately determined according to needs, but the reaction temperature should be at least 5~10" Ό below the boiling point of the chemical activator, and the time is 2~24 hours. Chemical activator The more intense the reaction with the carrier, the lower the reaction temperature and the longer the time. For example, when the chemical activator is titanium tetrachloride, the reaction temperature can be between -30 Ό and 126 ,, and the corresponding time is 12 to 2 hours.
在本发明方法的制备复合载体的步骤中， 所述镁化合物与所述修 饰载体之间的质量比为 1: 0.1-40, 优选 1: 1~10。 反应条件为 0~ 130Γ, 反应时间为 0.1~8小时。  In the step of preparing the composite carrier of the method of the present invention, the mass ratio between the magnesium compound and the modifying carrier is 1: 0.1-40, preferably 1: 1-10. The reaction conditions are 0 to 130 Torr, and the reaction time is 0.1 to 8 hours.
在本发明的负载化方法中， 所述镁化合物选自 ! ¾化镁、 烷氧基卤 化镁、 烷氧基镁， 或它们的混合物。 所述修饰载体与镁化合物作用的 过程中， 所述的四氢呋喃-醇混合溶剂选自四氢呋喃-脂肪醇、 四氢 呋喃 -环醇或四氢呋喃 -芳香醇或四氢呋喃 -乙醇。 所述鎂化合物优 选卤化镁， 最优选氯化镁。 所述催化剂负载化步骤中所用到的溶剂可以是本领域催化剂负载 化方法中常用的溶剂， 可以选自矿物油和不同的液态碳氢化合物。 典 型的溶剂是 5 到 12 个碳原子的烃类溶剂， 或是被氯原子取代的烃类 溶剂， 如二氯曱烷， 或醚基溶剂， 比如乙醚或四氢呋喃， 另外， 丙酮 或乙酸乙酯等也可使用。 该溶剂优选芳香族溶剂如曱苯和二曱苯； 或 是 6 到 10 个碳原子的脂肪族溶剂， 如己烷、 庚烷、 辛烷、 壬烷、 癸 烷及它们的异构体； 6到 12个碳原子的环脂肪族溶剂， 如己烷； 或者 是它们的混合物。 最优选四氢呋喃、 甲苯或己烷。 In the supported method of the present invention, the magnesium compound is selected from the group consisting of magnesium, alkoxymagnesium halide, magnesium alkoxide, or a mixture thereof. In the process of reacting the modified carrier with the magnesium compound, the tetrahydrofuran-alcohol mixed solvent is selected from the group consisting of tetrahydrofuran-fatty alcohol, tetrahydrofuran-cycloalcohol or tetrahydrofuran-aromatic alcohol or tetrahydrofuran-ethanol. The magnesium compound is preferably a magnesium halide, most preferably magnesium chloride. The solvent used in the catalyst loading step may be a solvent commonly used in catalyst loading methods in the art, and may be selected from mineral oils and different liquid hydrocarbons. Typical solvents are hydrocarbon solvents of 5 to 12 carbon atoms, or hydrocarbon solvents substituted by chlorine atoms, such as dichloromethane, or ether-based solvents such as diethyl ether or tetrahydrofuran, and acetone or ethyl acetate. Can also be used. The solvent is preferably an aromatic solvent such as toluene and dinonylbenzene; or an aliphatic solvent of 6 to 10 carbon atoms such as hexane, heptane, octane, decane, decane and isomers thereof; A cycloaliphatic solvent to 12 carbon atoms, such as hexane; or a mixture thereof. Most preferred is tetrahydrofuran, toluene or hexane.
在负载化过程中， 非茂金属烯烃聚合催化剂在溶剂中的浓度可以 是本领域催化剂负载化方法中常用的浓度， 一般为 0. 01 ~ 1 克催化剂 /亳升溶剂。  The concentration of the non-metallocene olefin polymerization catalyst in the solvent may be a concentration commonly used in the catalyst loading method in the art, and is generally 0.1 to 1 gram of catalyst per liter of solvent.
将非茂金属烯烃聚合催化剂溶解于溶剂中， 然后与复合载体进行 接触， 通过溶液法浸渍、 或等体积浸渍法， 或者先溶液浸渍、 过滤干 燥后再进行等体积浸渍的方法， 从而完成非茂金属催化剂在载体上的 负载化过程。  The non-metallocene olefin polymerization catalyst is dissolved in a solvent, and then contacted with the composite carrier, by solution impregnation, or an equal volume impregnation method, or by solution impregnation, filtration drying, and then an equal volume impregnation method, thereby completing the non-macro The loading process of the metal catalyst on the support.
进一步地， 对本发明负载方法的优化方案增加的两个步骤的意义 说明如下。  Further, the significance of the two steps added to the optimization scheme of the load method of the present invention is as follows.
金属氧化物表面一般都具有酸性的表面羟基， 该羟基可以与催化 剂反应而使之失活。 在使用之前， 载体要经历脱羟基过程， 其可以是 在真空或惰性气氛下， 焙烧而活化。 载体的活化是在 100- 100(TC、 惰 性气氛或减压条件下焙烧 l ~ 24h 完成的。 这里所说的惰性气氛是指 气体中仅含有及其微量或者不含有可与载体反应的组份。 焙烧条件优 选在 500 ~ 800 Χ、 ^或 Ar 气氛下持续 2 ~ 12h， 最优为 4 ~ 8h。 本领 域技术人员都知道， 经热活化的载体需要在惰性气氛下保存。  The surface of the metal oxide generally has an acidic surface hydroxyl group which can be reacted with the catalyst to inactivate it. Prior to use, the support is subjected to a dehydroxylation process which may be activated by calcination under vacuum or an inert atmosphere. The activation of the carrier is carried out at 100-100 (TC, inert atmosphere or under reduced pressure for 1 to 24 hours. The inert atmosphere referred to herein means that the gas contains only a trace amount and does not contain a component which can react with the carrier. The calcination conditions are preferably maintained in an atmosphere of 500 to 800 Torr, ^ or Ar for 2 to 12 hours, most preferably 4 to 8 hours. It is known to those skilled in the art that the thermally activated carrier needs to be stored under an inert atmosphere.
在本发明的方法中， 二氧化硅载体过热活化的目的是使载体表面 具有高活性的基团， 有报道（ J Am Chem Soc， 1996， 118: 401 )指出， 当干燥温度为 200°C ~ 500 Ό时， 易于除去的羟基基团被可逆地除去， 产生低反应活性的硅氧烷基团， 但在干燥温度超过 600 Ό的情况下， 羟基基团强制性地被除去， 转化成水， 产生具有高的环应力和很高反 应活性的硅氧烷基团。 也可以采用化学活化剂将载体表面的官能团转 化成其它不反应的硅氧烷基团。 ' 一般而言， 本发明的复合载体可以直接与非茂金属烯烃聚合催化 剂溶液进行接触， 从而在负载后得到本发明的高活性负载型非茂金属 烯烃聚合催化剂。 但是本研究发现， 如果要获得活性更优的负载型非 茂金属烯烃聚合催化剂， 优选对该复合载体经过进一步的处理， 以制 得修饰复合载体。 与由此而获得的额外活性相比， 这一处理步骤的成 本是微不足道的。 In the process of the present invention, the purpose of superheat activation of the silica support is to provide a highly active group on the surface of the support, as reported (J Am Chem Soc, 1996, 118: 401), when the drying temperature is 200 ° C ~ At 500 Torr, the easily removable hydroxyl group is reversibly removed, resulting in a low reactivity siloxane group, but at a drying temperature of more than 600 Torr, the hydroxyl group is forcibly removed and converted into water. A siloxane group having a high cyclic stress and a high reactivity is produced. Chemical activators can also be used to convert functional groups on the surface of the support to other unreacted siloxane groups. 'In general, the composite support of the present invention can be directly catalyzed by polymerization with non-metallocene olefins. The solution is contacted to obtain the highly active supported non-metallocene olefin polymerization catalyst of the present invention after the loading. However, this study found that if a more active supported non-metallocene olefin polymerization catalyst is to be obtained, the composite support is preferably subjected to further treatment to obtain a modified composite support. The cost of this processing step is negligible compared to the additional activity obtained thereby.
这一过程是将复合载体与化学处理剂相接触， 接触过程采用了溶 液浸渍法， 其中将复合载体浸渍于化学处理剂溶液中， 在搅拌下处理 In this process, the composite carrier is contacted with a chemical treatment agent, and the contact process is carried out by a solution impregnation method in which the composite carrier is immersed in a chemical treatment solution and treated under stirring.
0. 5 ~ 72h， 优选 2 ~ 24h， 最优选 2 ~ 6h。 0. 5 ~ 72h, preferably 2 ~ 24h, most preferably 2 ~ 6h.
化学处理剂选自铝氧浣、 烷基铝、 硼烷、 IVA、 IVB 或 VB族金属 的卤化物、 烷基化合物、 烷氧基化合物或！ ¾代烷基化合物中的一种或 多种。  The chemical treatment agent is selected from the group consisting of aluminide, alkyl aluminum, borane, IVA, IVB or VB metal halides, alkyl compounds, alkoxy compounds or! One or more of the 3⁄4 alkyl compounds.
IVA、 IVB 或 VB族金属的卤化物， 比如可举出四氯化硅、 四溴化 硅、 四碘化硅、 四氯化钛、 四溴化钛、 四碘化钛、 四氯化锆、 四溴化 锆、 四碘化锆、 四氯化铪、 四溴化铪、 四碘化铪、 氯化钒、 溴化钒、 碘化钒等。 优选四氯化钛、 四氯化硅、 四氯化锆、 氯化钒， 最优选四 氯化钛和四氯化硅。  The halide of the IVA, IVB or VB group metal may, for example, be silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or zirconium tetrachloride. Zirconium tetrabromide, zirconium tetraiodide, cerium tetrachloride, cerium tetrabromide, cerium tetraiodide, vanadium chloride, vanadium bromide, vanadium iodide, etc. Preferred are titanium tetrachloride, silicon tetrachloride, zirconium tetrachloride, vanadium chloride, and most preferred are titanium tetrachloride and silicon tetrachloride.
烷基铝比如可举出甲基铝、 乙基铝、 丙基铝、 异丁基铝或丁基铝 等。 优选乙基铝和异丁基铝， 最优选乙基铝；  Examples of the aluminum alkyl group include methyl aluminum, ethyl aluminum, propyl aluminum, isobutyl aluminum or butyl aluminum. Preferred are ethyl aluminum and isobutyl aluminum, most preferably ethyl aluminum;
卤代烷基化合物比如可举出一氯曱基铝、 二氯甲基铝、 一氯乙基 铝、 二氯乙基铝、 一氯丙基铝、 二氯丙基铝、 一氯异丁基铝、 二氯异 丁基铝、 一氯丁基铝、 二氯丁基铝等。 优选一氯乙基铝、 二氯乙基铝、 一氯异丁基铝和二氯异丁基铝， 最优选一氯乙基铝和二氯乙基铝。  Examples of the halogenated alkyl compound include monochloroindolyl aluminum, dichloromethylaluminum, ethylachloroethylaluminum, dichloroethylaluminum, monochloropropylaluminum, dichloropropylaluminum, and monochloroisobutylaluminum. Dichloroisobutyl aluminum, monochlorobutyl aluminum, dichlorobutyl aluminum, and the like. Preferred are monochloroethylaluminum, dichloroethylaluminum, monochloroisobutylaluminum and dichloroisobutylaluminum, most preferably monochloroethylaluminum and dichloroethylaluminum.
铝氧烷可以采用线性型（ I )和 /或环状型（ Π )铝氧烷的铝氧垸， 比如曱基铝氧烷、 乙基铝氧烷、 丙基铝氧烷、 异丁基铝氧烷、 丁基铝 氧烷或改性的甲基铝氧烷。 其中， 优选甲基铝氧烷、 乙基铝氧烷、 异 丁基铝氧垸或改性的甲基铝氧烷， 最优选曱基铝氧烷。  The aluminoxane may be a linear type (I) and/or a cyclic aluminoxane aluminoxane such as decyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, isobutyl aluminum. Oxyalkane, butyl aluminoxane or modified methyl aluminoxane. Among them, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or modified methylaluminoxane is preferred, and mercaptoaluminoxane is most preferred.
化学处理剂可以选择上述的多种组合， 两两组合， 如四氯化硅和 乙基铝、 四氯化硅和甲基铝氧烷、 四溴化硅和乙基铝、 四溴化硅和甲 基铝氧烷、 四氯化钛和乙基铝、 四氯化钛和曱基铝氧烷、 四氯化硅和 一氯乙基铝、 四氯化硅和二氯乙基铝、 四氯化钛和一氯乙基铝、 四氯 化钛和二氯乙基铝、 乙基铝和曱基铝氧烷、 一氯乙基铝和曱基铝氧烷、 二氯乙基铝和曱基铝氧烷。 三者组合， 如四氯化钛、 乙基铝和曱基铝 氧烷， 四氯化硅、 乙基铝和曱基铝氧烷， 等等。 化学处理剂的多种组 合优选两两组合， 如四氯化硅和乙基铝、 四氯化硅和甲基铝氧烷、 四 氯化钛和乙基铝、 四氯化钛和曱基铝氧烷、 乙基铝和曱基铝氧烷， 最 优选四氯化钛和乙基铝、 四氯化钛和曱基铝氧烷。 The chemical treatment agent may be selected from various combinations of the above, a combination of two, such as silicon tetrachloride and ethyl aluminum, silicon tetrachloride and methyl aluminoxane, silicon tetrabromide and ethyl aluminum, silicon tetrabromide and Methylaluminoxane, titanium tetrachloride and ethylaluminum, titanium tetrachloride and decyl aluminoxane, silicon tetrachloride and ethylaluminum chloride, silicon tetrachloride and ethylaluminum dichloride, tetrachloro Titanium and ethylaluminum chloride, titanium tetrachloride and ethylaluminum dichloride, ethylaluminum and mercaptoaluminoxane, monochloroethylaluminum and mercaptoaluminoxane, dichloroethylaluminum and sulfhydryl Aluminoxane. Combination of three, such as titanium tetrachloride, ethyl aluminum and bismuth aluminum Oxyalkane, silicon tetrachloride, ethyl aluminum and mercaptoaluminoxane, and the like. Various combinations of chemical treatment agents are preferably a combination of two, such as silicon tetrachloride and ethyl aluminum, silicon tetrachloride and methyl aluminoxane, titanium tetrachloride and ethyl aluminum, titanium tetrachloride and bismuth aluminum. The oxane, ethylaluminum and decyl aluminoxane are most preferably titanium tetrachloride and ethylaluminum, titanium tetrachloride and decyl aluminoxane.
化学处理剂与复合载体的反应可采用任何方法进行， 只要能使复 合载体与化学处理剂实现接触从而使其发生反应即可。 比如可举出以 下方法。  The reaction of the chemical treatment agent with the composite carrier can be carried out by any method as long as the composite carrier can be brought into contact with the chemical treatment agent to cause it to react. For example, the following methods can be mentioned.
将溶剂加入到复合载体中， 在溶剂的沸点以下进行搅拌， 再加入 化学处理剂或化学处理剂溶液， 如果采用的液态的化学处理剂可直接 加入， 如果采用的是固态化学处理剂， 应首先将固态的化学活化剂溶 解于此溶剂中然后加入。 加入方式为滴加。 反应 0. 5 - 24小时后过滤， 并采用相同的溶剂进行洗涤 1 ~ 8次后干燥。  Adding the solvent to the composite carrier, stirring below the boiling point of the solvent, and then adding a chemical treatment agent or a chemical treatment solution, if the liquid chemical treatment agent used can be directly added, if a solid chemical treatment agent is used, first A solid chemical activator is dissolved in this solvent and then added. The method of addition is dripping. The reaction was filtered after 0.5 to 24 hours, and washed with the same solvent for 1 to 8 times and then dried.
这里所述的溶剂也是任意的， 只要可以溶解化学处理剂， 或与化 学处理剂互溶即可， 比如选自 C5 - C12 的液态碳氢化合物、 芳香化合 物或 代碳氢化合物， 如戊烷、 己烷、 庚烷、 辛烷、 壬烷、 癸烷、 十 一烷、 十二烷、 环己烷、 曱苯、 乙苯、 二甲苯、 氯代戊烷、 氯代己垸、 氯代庚烷、 氯代辛烷、 氯代壬垸、 氯代癸烷、 氯代十一垸、 氯代十二 烷、 氯代环己烷、 氯代曱苯、 氯代乙苯、 氯代二曱苯等， 优选戊烷、 己烷、 癸烷、 环己烷、 甲苯， 最优选己烷和甲苯。  The solvent described herein is also arbitrary as long as it can dissolve the chemical treatment agent or is miscible with the chemical treatment agent, such as a liquid hydrocarbon selected from C5 to C12, an aromatic compound or a hydrocarbon-forming compound such as pentane or Alkane, heptane, octane, decane, decane, undecane, dodecane, cyclohexane, toluene, ethylbenzene, xylene, chloropentane, chlorohexan, chloroheptane, Chlorooctane, chlorohydrazine, chlorodecane, chlorodecane, chlorododecane, chlorocyclohexane, chlorophenylbenzene, chloroethylbenzene, chlorinated diphenylbenzene, etc. Pentane, hexane, decane, cyclohexane, toluene are preferred, and hexane and toluene are most preferred.
选用较高的反应温度有助于化学处理剂与复合载体的反应， 可以 减少反应时间。 反应温度随溶剂的不同而不同， 一般最高温度应选择 在低于溶剂沸点 5 ~ 10Ό以下， 反应时间没有特别的限制， 但在提高 反应温度的情况下， 反应时间可以适当越短。  The use of a higher reaction temperature facilitates the reaction of the chemical treatment with the composite support and reduces the reaction time. The reaction temperature varies depending on the solvent. Generally, the maximum temperature should be selected from the boiling point of the solvent below 5 to 10 Torr. The reaction time is not particularly limited, but the reaction time can be appropriately shortened in the case of increasing the reaction temperature.
其中， 复合载体与化学处理剂在接触时的配比为 1克： 1 ~ 100亳 摩尔， 优选的配比为 1克： 2 - 25亳摩尔。  Wherein, the ratio of the composite carrier to the chemical treatment agent in contact is 1 gram: 1 to 100 Torr, and the preferred ratio is 1 gram: 2 - 25 Torr.
复合载体在经过化学处理剂处理之后， 经过滤洗涤、 干燥和抽干 后， 制得修饰复合载体。  The composite carrier is subjected to a treatment with a chemical treatment agent, washed, washed, dried and dried to obtain a modified composite carrier.
在接下来的催化剂负载化步骤中， 所述修饰复合载体与所述非茂 金属烯烃聚合催化剂的盾量比为 1 : 0. 01 - 0. 50 , 优选质量比为 1 : 0. 05 - 0. 30。  In the next catalyst loading step, the ratio of the shield of the modified composite support to the non-metallocene olefin polymerization catalyst is 1:0.01 - 0. 50, and the preferred mass ratio is 1:0.05 - 0 30.
复合载体或修饰复合载体的洗涤、 过滤、 干燥和抽干可以采用本 领域熟知的方法， 如淋洗， 即在密闭或活性气氛下， 在一个不可通过 淋洗固体但可通过溶剂的砂芯漏斗上， 通过溶剂的反复冲洗以达到洗 涤过滤的目的； 或采用镌洗， 即静置除去上层液体， 然后再加入溶剂， 如此重复这些过程以达到洗涤过滤的目的； 或最为通常的方法是将需 要洗涤过滤的体系到入砂芯漏斗中， 通过抽滤作用抽去溶剂， 然后再 加入溶剂， 再抽滤， 从而达到洗涤过滤的目的 本发明优选抽滤方法。 洗涤过滤过程优选重复 2 ~ 4次。 Washing, filtering, drying and draining of the composite carrier or modified composite carrier can be carried out by methods well known in the art, such as rinsing, i.e., in a closed or active atmosphere, in a non-passible manner. The solid is rinsed but can be passed through the solvent core of the funnel, and the solvent is repeatedly washed to achieve the purpose of washing and filtering; or the rinsing is carried out, that is, the upper liquid is removed after standing, and then the solvent is added, so that the process is repeated to achieve the washing and filtering. Or the most common method is to wash the filtered system into the sand core funnel, remove the solvent by suction filtration, then add the solvent, and then suction filtration to achieve the purpose of washing and filtering. method. The washing and filtering process is preferably repeated 2 to 4 times.
将固体在温度约为 0 ~ 120 °C下进行减压干燥， 直到获得流动性的 催化剂载体粉末为止。 这个干燥过程时间的长短依赖于所用温度， 并 且与真空系统的能力和体系的密闭情况有关。  The solid is dried under reduced pressure at a temperature of about 0 to 120 ° C until a fluid catalyst carrier powder is obtained. The length of this drying process depends on the temperature used and is related to the capacity of the vacuum system and the containment of the system.
本领域的技术人员都知道， 以上所述的化学处理过程和非茂金属 烯烃聚合催化剂的负载化过程均需要在严格的无水无氧条件下进行， 这里所说的无水无氧条件是指体系中水和氧的含量持续小于 10ppm。  It is known to those skilled in the art that the above-mentioned chemical treatment process and the loading process of the non-metallocene olefin polymerization catalyst need to be carried out under strict anhydrous anaerobic conditions, and the anhydrous anaerobic conditions referred to herein mean The water and oxygen content of the system continues to be less than 10 ppm.
本领域的技术人员都知道， 对所获得的负载催化剂进行克分的洗 涤过滤、 干燥、 抽干是很重要的， 以便获得高活性和良好粒子形态的 聚合物。 其中， 洗涤过滤过程除去游离态的物质， 干燥和抽干可以获 得与反应物质的良好结合力。  It is known to those skilled in the art that it is important to perform a washing, drying, and drying of the obtained supported catalyst in grams to obtain a polymer having high activity and good particle morphology. Among them, the washing and filtering process removes the free substance, and drying and drying can obtain a good binding force with the reaction substance.
通过本发明的载体负载型非茂金属烯烃聚合催化剂的负载化方 法， 可以制造负载型非茂金属締烃聚合催化剂， 它是由非茂金属烯烃 聚合催化剂和载体构成的有机整体， 在与助催化剂共同组成催化体系 时， 可用于催化烯烃的均聚合或共聚合。 因此， 在一个实施方案中， 本发明涉及由本发明的载体负载型非茂金属烯烃聚合催化剂的负载化 方法所制造的负载型非茂金属烯烃聚合催化剂。  The supported non-metallocene hydrocarbon polymerization catalyst can be produced by the supported method of the support-supported non-metallocene olefin polymerization catalyst of the present invention, which is an organic whole composed of a non-metallocene olefin polymerization catalyst and a carrier, and a cocatalyst When used together to form a catalytic system, it can be used to catalyze the homopolymerization or copolymerization of olefins. Accordingly, in one embodiment, the present invention relates to a supported non-metallocene olefin polymerization catalyst produced by the supported method of the support-supported non-metallocene olefin polymerization catalyst of the present invention.
本发明的另一个目的是采用本发明的负载型非茂金属催化剂进行 烯烃的催化聚合， 或者催化不同嫦烃之间进行的共聚合。 本发明的新 方法克服了传统的多活性的非负载的齐格勒 -纳塔催化剂存在的聚合 产物规整度不好， 只能制造低端产品的缺点， 在采用本发明的单活性 的负载型非茂金属烯烃聚合催化剂进行烯烃的聚合或共聚合时， 可以 得到规整度更好的聚合产物， 从而满足高端产品生产的需要。  Another object of the present invention is to carry out catalytic polymerization of olefins or to carry out copolymerization between different terpene hydrocarbons using the supported non-metallocene catalyst of the present invention. The novel method of the present invention overcomes the disadvantages of the conventional multi-active unsupported Ziegler-Natta catalyst in that the polymerization product has poor regularity and can only produce low-end products, and adopts the single-active load type of the present invention. When the non-metallocene olefin polymerization catalyst is used for the polymerization or copolymerization of an olefin, a polymerization product having a better degree of regularity can be obtained, thereby meeting the needs of high-end product production.
为了完成上述的发明任务， 本发明所涉及的技术方案是： 一种烯 烃聚合和共聚合方法， 包括以下步骤：  In order to accomplish the above inventive task, the technical solution to which the present invention relates is: An olefin polymerization and copolymerization method comprising the following steps:
采用本发明的负载型非茂金属烯烃聚合催化剂， 与助催化剂组成 催化体系； 在聚合反应条件下， 向聚合反应器中引入聚合单体和 /或共聚合 单体， 进行烯烃聚合和 /或共聚合。 Using the supported non-metallocene olefin polymerization catalyst of the present invention, and a cocatalyst to constitute a catalytic system; The polymerization monomer and/or the copolymerization monomer are introduced into the polymerization reactor under polymerization conditions to carry out olefin polymerization and/or copolymerization.
采用本发明的负载型非茂金属烯烃聚合催化剂为主催化剂， 在助 催化剂作用下， 可以用于催化烯烃的聚合和共聚合。 这里所说的烯烃 选自 C2 - C10烯烃、 双烯烃或环烯烃， 如乙烯、 丙烯、 1 -丁烯、 1 - 己烯、 1 -庚烯、 4 -甲基- 1 -戊烯、 1 -辛烯、 1 -癸烯、 1 -十一烯、 1 -十二烯、 1 -环戊烯、 降水片烯、 降冰片二烯、 或苯乙烯、 1， 4- 丁二烯、 2， 5 -戊二烯、 1， 6 -己二烯、 1， 7-辛二烯， 或含功能性 基团的有机单体， 如醋酸乙烯、 丙烯酸甲酯、 丙烯酸乙酯、 丙烯酸丁 酯。 需要在这里指出的是， 本发明所说的聚合是指单一的含有双键的 烯烃、 双烯烃、 环締烃或者含功能性基团的有机单体进行的均聚合， 而共聚合是指两种， 或者两种以上的含有双键的烯烃、 双烯烃、 环烯 烃或者含功能性基团的有机单体之间所进行的聚合过程。  The supported non-metallocene olefin polymerization catalyst of the present invention is used as a main catalyst, and can be used for catalyzing the polymerization and copolymerization of olefins under the action of a cocatalyst. The olefin referred to herein is selected from a C2-C10 olefin, a diolefin or a cyclic olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1- Octene, 1-decene, 1-undecene, 1-dodecene, 1-cyclopentene, norbornene, norbornadiene, or styrene, 1, 4-butadiene, 2, 5 - pentadiene, 1,6-hexadiene, 1,7-octadiene, or a functional group-containing organic monomer such as vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate. It is to be noted herein that the polymerization referred to in the present invention means a homopolymerization of a single double bond-containing olefin, a diolefin, a cyclic hydrocarbon or a functional group-containing organic monomer, and the copolymerization means two , or a polymerization process carried out between two or more olefins, diolefins, cyclic olefins or functional organic groups containing a double bond.
聚合单体优选乙烯， 与乙烯进行共聚合的共聚单体优选西烯、 1- 丁烯或 1-己烯。  The polymerizable monomer is preferably ethylene, and the comonomer copolymerized with ethylene is preferably decene, 1-butene or 1-hexene.
作为本发明催化体系中的助催化剂， 选自烷基铝、 铝氧烷、 路易 斯酸、 硼氟烷、 烷基硼或烷基硼铵盐。  As a cocatalyst in the catalytic system of the present invention, it is selected from the group consisting of aluminum alkyls, aluminoxanes, Lewis acids, borofluorocarbons, alkyl boron or alkyl boron ammonium salts.
一般来说， 铝氧烷可以采用前述的线性型 （ I )和 /或环状型铝氧 烷（ Π ) 的铝氧烷。  In general, the aluminoxane may be the aluminoxane of the above linear type (I) and/or cyclic aluminoxane (?).
烷基铝或烷基硼为具有如下通式 （ffl ) 的化合物：  The aluminum alkyl or alkyl boron is a compound having the following formula (ffl):
N (R) 3 m N (R) 3 m
其中： N为铝或硼， R与结构 （ I ) 和（ Π ) 中定义相同， 三个 R 基团中的每一个可以相同， 也可以不同。 其具体实例包括三甲基铝、 三乙基铝、 三异丁基铝、 三丙基铝、 三丁基铝、 二曱基氯化铝、 三异 丙基铝、 三仲丁基铝、 三环戊基铝、 三戊基铝、 三异戊基铝、 三己基 铝、 乙基二甲基铝、 甲基二乙基铝、 三戊基铝、 三对 -曱苯基铝、 二 甲基铝曱醇益、 二甲基铝乙醇盐、 三曱基铵四苯基铝、 三曱基硼、 三 乙基硼、 三异丁基硼、 三丙基硼、 三丁基硼或三甲基铵四苯基硼； 而路易斯酸、 硼氟烷、 垸基硼或垸基硼铵盐则是指具有如下通式 ( IV ) 的化合物：  Wherein: N is aluminum or boron, R is the same as defined in structures (I) and (Π), and each of the three R groups may be the same or different. Specific examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimercapto aluminum chloride, triisopropyl aluminum, tri-sec-butyl aluminum, and three Cyclopentyl aluminum, triamyl aluminum, triisoamyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triamyl aluminum, tri-p-phenylene aluminum, dimethyl Aluminium decyl alcohol, dimethyl aluminum ethoxide, trimethyl ammonium tetraphenyl aluminum, trimethyl boryl, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron or trimethyl Ammonium tetraphenylboron; and a Lewis acid, a borofluoroalkane, a decyl boron or a decyl boronium ammonium salt refers to a compound having the following general formula (IV):
[L-H]+ [NE4]— 或 [L]+ [NEJ- IV [LH] + [NE 4 ] — or [L] + [NEJ- IV
其中 L为中性或阳性的离子型路易斯酸， H为氢原子， N为铝或硼， 各个 E可以相同或不同， 为具有 6 ~ 12个碳原子的芳基， 其中有一个 以上的氢被 素原子、 烷氧基或苯氧基所取代。 其具体实例包括三甲 基铵四苯基硼、 三甲基铵四 （对-曱苯基）硼、 三丁基铵四 （五氟苯 基）基硼、 三甲基膦四苯基硼、 三甲基铵四苯基铝、 三丙基铵四苯基 铝、 三曱基铵四 （对-甲苯基）铝、 三乙基铵四 （邻， 对-二曱基苯 基）铝、 三丁基铵四 （对-三氟甲基苯基）铝、 三曱基铵四 （对-三 氟甲基苯基）铝、 三丁基铵四 （五氣苯基）铝、 N， N -二乙基苯胺四 苯基铝、 N, N -乙基苯胺四（五氟苯基）铝或二乙基铵四 （五氟苯基） 铝等。 Wherein L is a neutral or positive ionic Lewis acid, H is a hydrogen atom, and N is aluminum or boron. Each E may be the same or different and is an aryl group having 6 to 12 carbon atoms in which one or more hydrogens are substituted by a phenol atom, an alkoxy group or a phenoxy group. Specific examples thereof include trimethylammonium tetraphenylboron, trimethylammonium tetra(p-nonylphenyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, trimethylphosphinetetraphenylboron, Trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, triammonium ammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o-, p-diphenylphenyl)aluminum, three Butyl ammonium tetrakis(p-trifluoromethylphenyl)aluminum, trimethylammonium tetrakis(p-trifluoromethylphenyl)aluminum, tributylammonium tetrakis(pentaphenoxyphenyl)aluminum, N,N- Diethylaniline tetraphenylaluminum, N,N-ethylaniline tetrakis(pentafluorophenyl)aluminum or diethylammonium tetrakis(pentafluorophenyl)aluminum.
本发明烯烃聚合和共聚合方法中所用的助催化剂优选铝氧烷， 最 优选甲基铝氧烷。  The cocatalyst used in the olefin polymerization and copolymerization process of the invention is preferably an aluminoxane, most preferably methylaluminoxane.
本发明的负载型非茂金属烯烃聚合催化剂在用于催化烯烃聚合和 共聚令时可以采用各种方法， 这类方法的具体实例包括淤浆法、 乳液 法、 溶液法、 本体法和气相法， 本发明的负载型非茂金属烯烃聚合催 化剂特别适用于气相法和淤浆法， 最适合于淤浆法。  The supported non-metallocene olefin polymerization catalyst of the present invention may be subjected to various methods for catalyzing the polymerization of olefins and copolymerization. Specific examples of such a method include a slurry method, an emulsion method, a solution method, a bulk method, and a gas phase method. The supported non-metallocene olefin polymerization catalyst of the present invention is particularly suitable for use in gas phase processes and slurry processes, and is most suitable for slurry processes.
需要采用溶剂时， 本发明的烯烃聚合或共聚合中所用到的聚合反 应用溶剂可以是本领域进行这类烯烃聚合或共聚合时所常用的溶剂， 可以是矿物油和不同的液态碳氢化合物。 典型的溶剂是 5 到 12 个碳 原子的烃类溶剂， 或是被氯原子取代的烃类溶剂， 如二氯甲烷， 或醚 基溶剂如乙醚或四氢呋喃， 另外， 丙酮或乙酸乙酯等也可使用。 优选 芳香族溶剂， 比如曱苯和二曱苯； 或是 6 到 10 个碳原子的脂肪族溶 剂， 如己烷、 庚烷、 辛烷、 壬烷、 癸烷及它们的异构体； 6到 12个碳 原子的环脂肪族溶剂， 如己烷； 或者是它们的混合物。 最优选己烷作 为本发明的聚合反应用溶剂。  When a solvent is required, the solvent for polymerization used in the polymerization or copolymerization of the olefin of the present invention may be a solvent commonly used in the field for the polymerization or copolymerization of such an olefin, and may be a mineral oil and a different liquid hydrocarbon. . Typical solvents are hydrocarbon solvents of 5 to 12 carbon atoms, or hydrocarbon solvents substituted with chlorine atoms, such as dichloromethane, or ether-based solvents such as diethyl ether or tetrahydrofuran, and acetone or ethyl acetate. use. Preferred are aromatic solvents such as toluene and diphenylbenzene; or aliphatic solvents of 6 to 10 carbon atoms such as hexane, heptane, octane, decane, decane and their isomers; A cycloaliphatic solvent of 12 carbon atoms, such as hexane; or a mixture thereof. Most preferably, hexane is used as the solvent for the polymerization reaction of the present invention.
将本发明的负载型非茂金属催化剂与助催化剂引入到聚合反应容 器中的方式是个很关键的技术参数。 引入方式可以是先向本发明的负 载型催化剂中加入聚合反应用溶剂， 形成一定浓度的催化剂悬浮液， 然后加入助催化剂， 形成催化体系， 然后加入到聚合反应容器中， 也 可以将催化剂的悬浮液与助催化剂分别加入到聚合反应容器中， 这种 分别加入的方式即， 可以是先将催化剂的悬浮液加入到聚合反应容器 中， 然后再将助催化剂加入到聚合反应容器中； 或者先将助催化剂加 入到聚合反应容器中， 然后再将催化剂的悬浮液加入到聚合反应容器 中； 抑或是将催化剂的悬浮液和助催化剂通过不同的加料口同时加入 到聚合反应容器中。 The manner in which the supported non-metallocene catalyst of the present invention and the cocatalyst are introduced into the polymerization vessel is a critical technical parameter. The introduction method may be that a solvent for polymerization is added to the supported catalyst of the present invention to form a certain concentration of the catalyst suspension, and then a cocatalyst is added to form a catalytic system, and then added to the polymerization reaction vessel, and the catalyst may be suspended. The liquid and the co-catalyst are respectively added to the polymerization reaction tank, and the separately added manner may be that the suspension of the catalyst is first added to the polymerization reaction vessel, and then the co-catalyst is added to the polymerization reaction vessel; or The cocatalyst is added to the polymerization vessel, and then the catalyst suspension is added to the polymerization vessel. Medium; or the catalyst suspension and cocatalyst are simultaneously added to the polymerization vessel through different feed ports.
在通常的情况下， 这几种加料方式并没有明显的区别， 都是本发 明明确可以采用的方式。 但是考虑到催化剂的悬浮液与助催化剂之间 的相互作用， 聚合反应器中的杂质含量情况， 以及聚合过程的经济状 况， 本发明优选的加料方式是先向负栽型催化剂加入聚合反应用溶 剂， 形成一定浓度的催化剂悬浮液， 然后加入助催化剂， 形成催化体 系， 然后加入到聚合反应容器中。 这种催化体系中负载型催化剂的浓 度和助催化剂浓度范围在本发明中并不需要明确， 但优选的浓度范围 是 0. 001 - 100克负载型催化剂 /升聚合反应用溶剂和 0. 0001 - 150克 助催化剂 /升聚合反应用溶剂， 最优选 0. 01 - 1 克负载型催化剂 /升聚 合反应用溶剂和 0. 0001 ~ 100克助催化剂 /升聚合反应用溶剂。  Under normal circumstances, there is no obvious difference between these types of feeding methods, which are all clearly applicable to the present invention. However, in view of the interaction between the suspension of the catalyst and the cocatalyst, the content of impurities in the polymerization reactor, and the economical state of the polymerization process, the preferred feeding method of the present invention is to first add a solvent for polymerization to the negative catalyst. A certain concentration of the catalyst suspension is formed, and then a cocatalyst is added to form a catalytic system, which is then added to the polymerization vessel. 0001 - The concentration of the supported catalyst and the concentration of the cocatalyst in the catalyst system is not required to be clarified in the present invention, but the preferred concentration range is 0. 001 - 100 g of supported catalyst / liter of solvent for polymerization and 0. 0001 - The solvent for the polymerization is preferably used in an amount of from 0.01 to 1 gram of the supported catalyst per liter of the solvent for the polymerization and from 0.001 to 100 g of the cocatalyst per liter of the solvent for the polymerization.
在进行本发明的烯烃聚合 /共聚合反应时， 如果反应需要在一定的 压力下进行， 则聚合反应压力为本领域在进行这类反应时的常规压 力， 一般在 0. 1 ~ l OMPa之间， 优选 0. 1 ~ 4MPa , 最优选 1 ~ 3MPa。 较 高的聚合压力可以加快负载型非茂金属催化剂催化烯烃聚合 /共聚的 速率， 得到高产量的聚合物， 但可能会导致聚合物形态变差， 得不到 粒子形态优良的、 干燥后可自由流动的聚合物粒子， 增加了后续过程 处理的难度和成本。 与此同时， 较低的聚合压力也会产生许多问题， 最主要的如活性问题， 可能会导致聚合过程的不经济。  In the case of the olefin polymerization/copolymerization of the present invention, if the reaction is required to be carried out under a certain pressure, the pressure of the polymerization is in the field of the conventional pressure in the field, generally between 0.1 to 1 OMPa. Preferably, it is 0.1 to 4 MPa, and most preferably 1 to 3 MPa. Higher polymerization pressure can accelerate the rate of olefin polymerization/copolymerization of supported non-metallocene catalysts, resulting in high yield of polymer, but may result in poor polymer morphology, excellent particle morphology, and freedom after drying. Flowing polymer particles increase the difficulty and cost of subsequent processing. At the same time, lower polymerization pressures can cause many problems, most importantly, activity problems, which can lead to uneconomical polymerization processes.
在本发明的烯烃聚合和共聚合方法中， 聚合温度条件为本领域中 的常规条件， 一般为 - 40Ό ~ 200 。 在较低的聚合温度下， 得到的 聚合活性是非常有限的， 可能会导致聚合过程的不经济， 而过高的聚 合温度可能会导致聚合物形态变差， 得不到粒子形态优良的、 干燥后 可自由流动的聚合物粒子， 增加了后续过程处理的难度和成本。 本发 明优选 10'C ~ 100 ， 最优选 40"C ~ 90Ό。  In the olefin polymerization and copolymerization method of the present invention, the polymerization temperature conditions are conventional conditions in the art, and are generally -40 Å to 200 Å. At lower polymerization temperatures, the polymerization activity obtained is very limited, which may lead to uneconomical polymerization. Excessive polymerization temperature may result in poor polymer morphology, excellent particle morphology, and dryness. The free-flowing polymer particles increase the difficulty and cost of subsequent processing. The present invention is preferably 10'C to 100, most preferably 40"C to 90".
在采用本发明的负载型非茂金属催化剂催化烯烃进行共聚反应 时， 共聚单体引入到聚合反应容器中的形式可以是间歇的， 也可以是 连续不间断的。 根据对聚合后共聚产品的需要， 共聚单体的引入量可 以为 0. 01 ~ 50% (相对于聚合产品总量而言） 。  In carrying out the copolymerization of an olefin by the supported non-metallocene catalyst of the present invention, the form in which the comonomer is introduced into the polymerization vessel may be intermittent or continuous. The amount of the comonomer introduced may be from 0.01 to 50% (relative to the total amount of the polymerized product), depending on the need for the copolymerized product after polymerization.
在本发明的烯烃聚合和共聚合方法中， 在反应需要搅拌时， 则锚 式搅拌桨、 推进式搅拌桨、 开启式搅拌桨或螺旋式搅拌桨等搅拌桨形 式都可以作为本发明的搅拌桨， 从而促进聚合物料的分散、 以及热量 和质量的传递。 优选推进式搅拌桨。 搅拌速率可以是 1 2000 转 /分 钟， 优选 100 ~ 600转 /分钟。 In the olefin polymerization and copolymerization method of the present invention, when the reaction requires agitation, agitating paddles such as an anchor paddle, a propeller paddle, an open paddle or a screw paddle are used. Both can be used as the agitating paddle of the present invention to promote dispersion of the polymer material, as well as transfer of heat and mass. A propulsion paddle is preferred. The agitation rate can be 12,000 rpm, preferably 100 to 600 rpm.
本发明的烯烃聚合和共聚合方法可以在氢气存在的条件下进行， 也可以在没有氢气存在的条件下进行。 如果需要， 氢气可以作为聚合 物分子量调节剂添加， 其分压可以是聚合压力的 0.01%~99%, 优选 氢气分压占聚合压力的 0.01% ~50%。  The olefin polymerization and copolymerization process of the present invention can be carried out in the presence of hydrogen or in the absence of hydrogen. If necessary, hydrogen may be added as a polymer molecular weight regulator, and the partial pressure may be from 0.01% to 99% of the polymerization pressure, and preferably the partial pressure of hydrogen is from 0.01% to 50% of the polymerization pressure.
如前所述， 本发明的负载型非茂金属烯烃聚合催化剂尤其适合于 淤浆法。  As described above, the supported non-metallocene olefin polymerization catalyst of the present invention is particularly suitable for the slurry method.
因此， 本发明的还一个目的是提供一种乙烯淤浆聚合方法， 该方 法采用了本发明的负载型非茂金属烯烃聚合催化剂与助催化剂组成的 催化体系。  Accordingly, it is still another object of the present invention to provide an ethylene slurry polymerization process which employs a catalytic system comprising a supported non-metallocene olefin polymerization catalyst of the present invention and a cocatalyst.
本发明乙烯淤浆聚合方法中采用的助催化剂与之前针对烯烃催化 聚合或共聚时所述的相同， 尤其可以选用铝氧烷或烷基铝， 或是两者 的混合物， 如甲基铝氧垸 (MA0) 、 乙基铝氧烷 （EA0) 、 异丁基铝氧 烷（IBA0)、三甲基铝（TMA)、三乙基铝（TEA)、三异丁基铝（TIBA)、 MAO-TEA, MAO- TMA等； 优选 MAO、 TEA或 TIBA。  The cocatalyst used in the ethylene slurry polymerization process of the present invention is the same as that previously described for the catalytic polymerization or copolymerization of olefins, and in particular, aluminoxane or alkylaluminum, or a mixture of the two, such as methylaluminoxane, may be used. (MA0), Ethyl Aluminoxane (EA0), Isobutyl Aluminoxane (IBA0), Trimethyl Aluminum (TMA), Triethyl Aluminum (TEA), Triisobutyl Aluminum (TIBA), MAO- TEA, MAO-TMA, etc.; preferably MAO, TEA or TIBA.
形成催化体系时， 当本发明负载型非茂金属烯烃聚合催化剂中的 过渡金属原子为 Ti 时， 助催化剂与负载型非茂金属催化剂配比为 A1 /Ti = 1: 1 - 1000 (摩尔比） ， 优选的配比为 Al/Ti = l: 1~ 500 (摩 尔比） ， 更优选的配比为 Al/Ti = l: 10~ 500 (摩尔比） 。  When the catalytic system is formed, when the transition metal atom in the supported non-metallocene olefin polymerization catalyst of the present invention is Ti, the ratio of the cocatalyst to the supported non-metallocene catalyst is A1 / Ti = 1: 1 - 1000 (molar ratio) The preferred ratio is Al/Ti = l: 1 to 500 (molar ratio), and the more preferable ratio is Al/Ti = l: 10 to 500 (molar ratio).
本发明乙烯淤浆聚合方法中采用的聚合温度是本领域的常规温 度， 一般为 10~100Ό， 优选 10~95"C， 更优选 30~95°C， 聚合压力 为 0.1 ~ 3. OMPa, 优选 0.1 ~ 2.0MPa。  The polymerization temperature used in the ethylene slurry polymerization method of the present invention is a conventional temperature in the art, and is generally 10 to 100 Torr, preferably 10 to 95"C, more preferably 30 to 95 ° C, and the polymerization pressure is 0.1 to 3. OMPa, preferably. 0.1 ~ 2.0MPa.
本发明的乙烯淤浆聚合包括： 乙烯均聚、 乙烯与 C3-C12 的烯烃 共聚合， 或在氢气存在下乙烯均聚、 乙烯与 C3- C12 的烯烃共聚合； C3-C12 可以是丙烯、 丁烯 -1、 戊烯- 1、 己烯- 1、 4 -甲基-戊烯 -1、 庚烯- 1、 辛烯- 1， 或降水片烯等。 其中， 优选丙烯、 丁烯- 1、 己烯- 1、 辛烯- 1和降水片烯， 最优选丙烯、 丁烯 - 1、 己烯- 1。  The ethylene slurry polymerization of the present invention comprises: ethylene homopolymerization, copolymerization of ethylene with C3-C12 olefin, or homopolymerization of ethylene in the presence of hydrogen, copolymerization of ethylene with C3-C12 olefin; C3-C12 may be propylene, butyl Alkene-1, pentene-1, hexene-1, 4-methyl-pentene-1, heptene-1, octene-1, or norbornene. Among them, propylene, butene-1, hexene-1, octene-1 and norbornene are preferred, and propylene, butene-1 and hexene-1 are most preferred.
为了调节聚合物的熔融指数， 通常在本发明的乙烯淤浆聚合过程 使用氢气作为链转移剂。使用的氢气量可占总气体量的 0.01 ~ 0.99 (体 积比） ， 优选 0.01 ~ 0.50 (体积比） 。 本发明的乙烯淤浆聚合方法中所用的溶剂是 5到 12个碳原子的烃 类溶剂， 或是被氯原子取代的烃类溶剂， 优选 6 到 12 个碳原子的芳 香族溶剂； 或是 6到 10个碳原子的脂肪族溶剂； 0到 12个碳原子的 环脂肪族溶剂， 或者是它们的混合物。 In order to adjust the melt index of the polymer, hydrogen is generally used as a chain transfer agent in the ethylene slurry polymerization process of the present invention. The amount of hydrogen used may be 0.01 to 0.99 (volume ratio) of the total gas amount, preferably 0.01 to 0.50 (volume ratio). The solvent used in the ethylene slurry polymerization method of the present invention is a hydrocarbon solvent of 5 to 12 carbon atoms, or a hydrocarbon solvent substituted by a chlorine atom, preferably an aromatic solvent of 6 to 12 carbon atoms; or 6 An aliphatic solvent of up to 10 carbon atoms; a cycloaliphatic solvent of 0 to 12 carbon atoms, or a mixture thereof.
另外， 本发明的乙烯淤浆聚合过程中未提到的其他事宜与之前针 对烯烃催化聚合或共聚时所述的相同。  Further, other matters not mentioned in the polymerization of the ethylene slurry of the present invention are the same as those previously described for the catalytic polymerization or copolymerization of olefins.
发明的详细说明  Detailed description of the invention
以下采用实施例进一步详细地说明本发明， 但本发明不限于这些 实施例。  The invention is further illustrated by the following examples, but the invention is not limited to the examples.
聚合物堆密度测定参照标准 GB 1636-79进行。 负载型非茂金属烯烃聚合催化剂的制备实施例 实施例 1 - 1， 高活性复合载体负载的非茂金属催化剂的负载化方 法， 主要包括以下步骤： Λ 载体多孔的固体采用二氧化硅 Grace 955 , 将二氧化硅在 500 ~ 800 °C、 N2或 Ar气氛下持续干燥或焙烧 4 - 8h。 经热活化的脱羟基二氧化硅 需要在惰性气氛下保存。 The polymer bulk density was determined by reference to GB 1636-79. Preparation Examples of Supported Non-metallocene Olefin Polymerization Catalyst Example 1 - 1, a high activity composite support supported non-metallocene catalyst loading method, mainly comprising the following steps: Λ Carrier porous solid using silica Grace 955 The silica is continuously dried or calcined at 500 to 800 ° C, N 2 or Ar for 4-8 hours. The thermally activated dehydroxylated silica needs to be stored under an inert atmosphere.
化学活化剂采用四氯化钛； 将活化后的载体与四氯化钛作用， 过滤 洗涤干燥和抽干后得到修饰载体。四氯化钛与二氧化硅的质量比为 1 : 40;  The chemical activator is titanium tetrachloride; the activated carrier is reacted with titanium tetrachloride, filtered, washed and dried to obtain a modified carrier. The mass ratio of titanium tetrachloride to silicon dioxide is 1:40;
将氯化镁溶解于四氢呋喃 -乙醇'; ¾合体系中形成溶液， 再将修饰载 体加入到此溶液中， 在 0 ~ 60 搅拌条件下充分反应形成透明体系。 时 间为 1 ~ 48小时， 优选 4 - 24小时。 经过滤洗涤、 干燥和抽干后制得复 合载体。 氯化镁含水量应小于盾量的 1 %， 平均粒径为 1 ~ ΙΟΟμιη, 优逸 20 ~ 40μιη; 比表面积为 5 ~ l OOmVg, 优选 5 ~ 30 m2/g。 The magnesium chloride is dissolved in tetrahydrofuran-ethanol'; a solution is formed in the system, and the modified carrier is added to the solution, and fully reacted under a stirring condition of 0 to 60 to form a transparent system. The time is from 1 to 48 hours, preferably from 4 to 24 hours. The composite carrier is prepared by washing, drying and drying. The water content of magnesium chloride should be less than 1% of the shield volume, and the average particle size is 1 ~ ΙΟΟμιη, Youyi 20 ~ 40μιη; the specific surface area is 5 ~ l OOmVg, preferably 5 ~ 30 m 2 /g.
将无水氯化镁加入到四氢呋喃 -醇混合体系中搅拌形成溶液， 提高 搅拌温度有助于缩短溶解过程， 温度范围从 0 ~ 60Ό， 优选 40 ~ 50°C：。  The anhydrous magnesium chloride is added to the tetrahydrofuran-alcohol mixture system to form a solution, and the stirring temperature is increased to help shorten the dissolution process, and the temperature ranges from 0 to 60 Torr, preferably 40 to 50 ° C:.
采用曱基铝氧烷对复合载体进行化学修饰， 得到修饰复合载体； 将具有以下结构的非茂金属烯烃聚合催化剂溶解于溶剂中：
Figure imgf000027_0001
The composite support is chemically modified with mercaptoaluminoxane to obtain a modified composite support; a non-metallocene olefin polymerization catalyst having the following structure is dissolved in a solvent:
Figure imgf000027_0001
然后与复合载体或修饰复合载体接触后洗涤过滤、 干燥抽干成负载型非 茂金属催化剂。 Then, it is contacted with the composite carrier or the modified composite carrier, washed, filtered, and dried to be a supported non-metallocene catalyst.
由此所得到的复合载体、 修饰复合载体和负载型非茂金属催化剂复 制载体形态， 都是干的、 可流动的固体粉末。  The thus obtained composite carrier, modified composite carrier and supported non-metallocene catalyst replica carrier form are both dry, flowable solid powders.
本发明所涉及的 "非茂金属烯烃聚合催化剂" 是同领域技术人员公 知的， 所以本实施例中的非茂金属烯烃聚合催化剂可以用任意一个同类 催化剂替换， 其反应步驟基本相同。 实施例 1-1-1， 与实施例 1-1基本相同， 但有如下改变：  The "non-metallocene olefin polymerization catalyst" according to the present invention is well known to those skilled in the art, so that the non-metallocene olefin polymerization catalyst in this embodiment can be replaced with any one of the same type of catalysts, and the reaction steps are substantially the same. Embodiment 1-1-1 is basically the same as Embodiment 1-1, but with the following changes:
将氟化镁溶解于四氢呋喃 -甲醇混合体系中形成溶液。  The magnesium fluoride was dissolved in a tetrahydrofuran-methanol mixed system to form a solution.
实施例 1-1-2， 与实施例 1-1基? M目同， 但有如下改变：  Example 1-1-2, the same as Example 1-1, but with the following changes:
将 乜镁溶解于四氢呋喃 -丙醇混合体系中形成溶液。 实施例 1-1-3， 与实施例 1-1基^目同， 但有如下改变：  The magnesium cerium is dissolved in a tetrahydrofuran-propanol mixed system to form a solution. Examples 1-1-3 are the same as those of the embodiment 1-1, but with the following changes:
将溴化镁溶解于四氢呋喃 -丁醇混合体系中形成溶液。 实施例 1-1-4， 与实施例 1-1基本相同， 但有如下改变：  The magnesium bromide is dissolved in a tetrahydrofuran-butanol mixed system to form a solution. Embodiments 1-1-4 are basically the same as Embodiment 1-1, but with the following changes:
化学活化剂采用金属卤化物氯化锆； 将活化后的载体与氯化锆作用， 过滤洗涤干燥和抽干后得到修饰载体。 氯化锆与二氧化硅的质量比为 1: The chemical activator uses a metal halide zirconium chloride; the activated carrier is reacted with zirconium chloride, filtered, washed and dried to obtain a modified carrier. The mass ratio of zirconium chloride to silicon dioxide is 1:
40; 40;
将氯化镁溶解于四氢呋喃 -戊醇混合体系中形成溶液。 实施例 1-1-5 , 与实施例 1-1基 «目同， 但有如下改变：  Magnesium chloride is dissolved in a tetrahydrofuran-pentanol mixed system to form a solution. Example 1-1-5, with the embodiment 1-1 base «the same, but with the following changes:
将氯化镁溶解于四氢呋喃 -己醇混合体系中形成溶液。 实施例 1-1-6， 与实施例 1-1基^目同， 但有如下改变：  Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution. Examples 1-1-6 are the same as those of the embodiment 1-1, but with the following changes:
化学活化剂采用金属卤化物溴化锆； 将活化后的载体与溴化锆作用， 过滤洗涤干燥和抽干后得到修饰载体。 溴化锆与二氧化硅的质量比为 1: 将氯化镁溶解于四氢呋喃 -己醇混合体系中形成溶液。 实施例 1-1-7， 与实施例 1-1基本相同， 但有如下改变： The chemical activator uses a metal halide zirconium bromide; the activated support is reacted with zirconium bromide, filtered, washed and dried to obtain a modified support. The mass ratio of zirconium bromide to silicon dioxide is 1: Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution. Embodiments 1-1-7 are basically the same as Embodiment 1-1, but with the following changes:
化学活化剂采用金属卤化物氟化铝； 将活化后的载体与氟化铝作用， 过滤洗涤干燥和抽干后得到修饰载体。 氟化铝与二氧化硅的质量比为 1: The chemical activator uses a metal halide aluminum fluoride; the activated carrier is reacted with aluminum fluoride, filtered, washed and dried to obtain a modified carrier. The mass ratio of aluminum fluoride to silicon dioxide is 1:
40; 40;
将氯化镁溶解于四氢呋喃 -庚醇混合体系中形成溶液。 实施例 1-2， 与实施例 1-1基^目同， 但有如下改变：  Magnesium chloride is dissolved in a tetrahydrofuran-heptanol mixed system to form a solution. The embodiment 1-2 is the same as the embodiment 1-1, but has the following changes:
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000028_0001
Figure imgf000028_0001
载体二氧化硅的热活化条件是： 100- 1000°C、 减压条件下， 干燥或 焙烧 2 ~ 12h;  The thermal activation condition of the carrier silica is: 100-1000 ° C, under reduced pressure, dried or calcined for 2 ~ 12 h;
氯化镁与二氧化硅的质量比为 1 ： 0. 1;  The mass ratio of magnesium chloride to silicon dioxide is 1: 0. 1;
化学活化剂采用四氯化钛；  The chemical activator uses titanium tetrachloride;
经过热活化的二氧化硅与四氯化钛溶液反应一定时间后， 过滤洗涤 干燥得到修饰载体。 二氧化硅与四氯化钛溶液反应时间的长短对影响到 四氯化钛在二氧化硅表面的含量， 长时间反应将可以得到高四氯化钛含 量的二氧化硅载体， 短时间则相反。 经本发明发现， 0. 5 ~ 24h可以得到 比较优的结果， 最优是采用反应 l ~ 6h。 温度在这里没有限定， 但是很 明显， 在较低的温度条件下， 四氯化钛因汽化而离开反应体系的损耗量 是很小的， 这有利于四氯化钛在二氧化硅载体上的负载效率， 提高四氯 化钛的含量。 对于催化烯烃聚合催化剂， 高四氯化钛含量将有助于提高 催化剂的催化烯烃聚合活性， 但在实际的操作过程中， 提高四氯化钛的 含量并不容易， 一般需要在低温下长时间的条件下， 采用纯的四氯化钛 来浸泡载体， 或者采用多次浸泡载体。 本发明的特色之一就是可以在温 和的条件下提供一种高的四氯化钛含量的载体。 四氯化钛溶液可以是任 意可与四氯化钛形成性能稳定、 性质均一的四氯化钛和溶剂混合物， 优 选四氯化钛的己烷溶液。 过滤洗涤溶剂最优选择己坑溶剂； After the thermally activated silica is reacted with the titanium tetrachloride solution for a certain period of time, it is washed and dried by filtration to obtain a modified carrier. The reaction time of silica and titanium tetrachloride solution affects the content of titanium tetrachloride on the surface of silica. Long-term reaction will result in a silica carrier with a high content of titanium tetrachloride. In a short time, the opposite is true. . According to the invention, the superior result can be obtained from 0.5 to 24 hours, and the optimum is to use the reaction for l ~ 6h. The temperature is not limited here, but it is obvious that at lower temperature conditions, the amount of loss of titanium tetrachloride from the reaction system due to vaporization is small, which is advantageous for the titanium tetrachloride on the silica carrier. Load efficiency, increase the content of titanium tetrachloride. For the catalytic olefin polymerization catalyst, the high titanium tetrachloride content will help to increase the catalytic olefin polymerization activity of the catalyst, but in the actual operation process, it is not easy to increase the content of titanium tetrachloride, and generally needs to be at a low temperature for a long time. Under the conditions, pure titanium tetrachloride is used to soak the carrier, or multiple times to soak the carrier. One of the features of the present invention is that it provides a high titanium tetrachloride content carrier under mild conditions. The titanium tetrachloride solution can be any titanium tetrachloride and solvent mixture which can form stable properties and uniform properties with titanium tetrachloride. A solution of titanium tetrachloride in hexane was chosen. Filtering the washing solvent to select the pit solvent;
干燥后的修饰二氧化硅载体是干的可流动的粉末。  The dried modified silica support is a dry flowable powder.
四氢呋喃一醇混合体系改为四氢呋喃 -环醇， 本实施例为四氢呋喃 -环己醇；  The tetrahydrofuran-ol mixed system is changed to tetrahydrofuran-cycloalcohol, and this embodiment is tetrahydrofuran-cyclohexanol;
其中溶解的镁化合物改为烷氧基卤化镁， 本实施例为 MgC10CH3; 对复合载体进行化学修饰的修饰剂改为烷基铝， 例如： 三甲基铝、 三乙基铝、 三异丁基铝等。 实施例 1-2-1， 与实施例 1- 相同， 但有如下改变： The dissolved magnesium compound is changed to alkoxymagnesium halide, this embodiment is MgC10CH 3 ; the modifier for chemically modifying the composite carrier is changed to alkyl aluminum, for example: trimethyl aluminum, triethyl aluminum, triisobutyl Base aluminum and so on. Example 1-2-1, which is the same as Example 1 but with the following changes:
四氢呋喃 -醇混合体系改为四氢呋喃-环戊醇；  The tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclopentanol;
镁化合物改为 MgC10CH2CH3; The magnesium compound was changed to MgC10CH 2 CH 3 ;
对复合载体进行化学修饰的修饰剂改为三乙基铝。 实施例 1-2-2， 与实施例 1-2基本相同， 但有如下改变：  The modifier which chemically modified the composite carrier was changed to triethylaluminum. Embodiment 1-2-2 is basically the same as Embodiment 1-2, but with the following changes:
四氢呋喃 -醇混合体系改为四氢呋喃 -环辛醇；  The tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclooctyl alcohol;
镁化合物改为 MgC10C4H9； The magnesium compound was changed to MgC10C 4 H 9 ;
对复合载体进行化学修饰的修饰剂改为三异丁基铝。 实施例 1-2-3， 与实施例 1-2基本相同， 但有如下改变：  The modifier which chemically modified the composite carrier was changed to triisobutylaluminum. Embodiment 1-2-3 is basically the same as Embodiment 1-2, but with the following changes:
镁化合物改为 MgBrOCH3。 The magnesium compound was changed to M g BrOCH 3 .
实施例 1-2-4 , 与实施例 1-2基本相同， 但有如下改变：  Example 1-2-4 is basically the same as Embodiment 1-2, but with the following changes:
镁化合物改为 MgBrOCH2CH3。 实施例 1-2-5， 与实施例 1-2基本相同， 但有如下改变： The magnesium compound was changed to M g BrOCH 2 CH 3 . Example 1-2-5 is basically the same as Embodiment 1-2, but with the following changes:
镁化合物改为 MgBrOC4H9。 实施例 1-3 , 与实施例 1-1基本相同， 但有如下改变： The magnesium compound was changed to M g BrOC 4 H 9. Embodiment 1-3 is basically the same as Embodiment 1-1, but with the following changes:
载体二氧化硅的热活化条件是： Ar气氛下干燥或焙烧 1 ~ 24h进行; 氯化镁与二氧化硅的质量比为 1 ： 10。 实施例 1-4， 与实施例 1-1 ~ 1 - 3基本相同， 但有如下改变： 二氧化硅不进行热活化， 直接与氯化镁作用得到复合载体； 氯化镁 与二氧化硅的质量比为 1 : 1。 实施例 1-5, 与实施例 1-1 ~ 1-3基本相同， 但有如下改变： The thermal activation conditions of the supported silica are: drying or calcination in an Ar atmosphere for 1 to 24 hours; the mass ratio of magnesium chloride to silicon dioxide is 1:10. Examples 1-4 are substantially the same as those of Examples 1-1 to 1-3, but with the following changes: Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier; The mass ratio to silica is 1:1. Embodiments 1-5 are basically the same as Embodiments 1-1 to 1-3, but with the following changes:
复合载体直接与非茂金属烯烃聚合催化剂反应， 不与化学处理剂作 用， 不需制成修饰复合载体。 实施例 1-6， 与实施例 1-1 ~ 1-3基本相同， 但同时有如下两个改变： 二氧化硅不进行热活化， 直接与氯化镁作用得到复合载体； 氯化镁 与二氧化硅的盾量比为 1 ： 1;  The composite support reacts directly with the non-metallocene olefin polymerization catalyst and does not act with a chemical treatment agent, and does not require a modified composite support. Examples 1-6, which are basically the same as Examples 1-1 to 1-3, but have the following two changes: Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier; Shield of magnesium chloride and silica The ratio is 1:1;
复合载体直接与非茂金属烯烃聚合催化剂反应， 不与化学处理剂作 用， 不需制成修饰复合载体。 实施例 1-7， 与实施例 1-1 ~ 1-3或 1-4 - 1-6基本相同， 但有如下改 变：  The composite support reacts directly with the non-metallocene olefin polymerization catalyst and does not act with a chemical treatment agent, and does not require a modified composite support. Embodiments 1-7 are basically the same as Embodiments 1-1 to 1-3 or 1-4 - 1-6, but with the following changes:
作为载体的多孔固体改为： ΠΑ、 ΙΠΑ、 WA族和 IVB族金属氧化物在 内的固体无机氧化物或卤化物， 如： 氧化铝、 氧化镁、 氧化钛、 氧化锆、 氧化钍、 氯化镁。 实施例 1-8， 与实施例 1-1 ~ 1-3或 1-4 ~ 1-6基本相同， 但有如下改 变：  The porous solid as a carrier is changed to: solid inorganic oxides or halides of lanthanum, cerium, group wa and group IVB metal oxides, such as: alumina, magnesia, titania, zirconia, cerium oxide, magnesium chloride. Embodiments 1-8 are basically the same as Embodiments 1-1 to 1-3 or 1-4 to 1-6, but with the following changes:
用于制备修饰复合载体的化学处理剂改为： 甲基铝氧烷与四氯化钛 两者的混合物；  The chemical treatment agent for preparing the modified composite carrier is changed to: a mixture of methyl aluminoxane and titanium tetrachloride;
四氢呋喃-醇混合体系改为四氢呋喃-芳香醇， 例如： 四氢呋喃- 苯基甲醇、 四氢呋喃-苯基乙醇、 四氢呋喃-苯基丁醇、 四氢呋喃-萘 基曱醇、 四氢呋喃 -萘基乙醇、 四氢呋喃-萘基丁醇、 等；  The tetrahydrofuran-alcohol mixed system is changed to tetrahydrofuran-aromatic alcohol, for example: tetrahydrofuran-phenylmethanol, tetrahydrofuran-phenylethanol, tetrahydrofuran-phenylbutanol, tetrahydrofuran-naphthylsterol, tetrahydrofuran-naphthylethanol, tetrahydrofuran-naphthyl Butanol, etc.;
其中溶解的鎂化合物改为：烷氧基镁，例如： Mg (0CH3) 2、Mg (0 CH2CH3) 2、 Mg (OC4H9) 2等。 负载型非茂金属烯烃聚合催化剂的制备实施例还包括以下的实施 例。 实施例 1-1 在以下实施例中， 高活性复合载体负载的非茂金属催化剂的负载 化方法主要包括以下步驟。 The dissolved magnesium compound is changed to: alkoxymagnesium, for example, Mg (0CH 3 ) 2 , Mg (0 CH 2 CH 3 ) 2 , Mg (OC 4 H 9 ) 2 or the like. The preparation examples of the supported non-metallocene olefin polymerization catalyst further include the following examples. Example 1-1 In the following examples, the loading method of the high activity composite support supported non-metallocene catalyst mainly comprises the following steps.
负载型催化剂的制备过程：  Preparation process of supported catalyst:
载体的热活化： 取 ES70型二氧化硅（Ineos公司产品）在氮气气 氛 650°C下恒温 6h流化过热活化。  Thermal activation of the carrier: ES70 type silica (product of Ineos) was subjected to fluidization at 650 ° C for 6 hours under hydrothermal activation.
修饰载体的制备： 称取 2g过热活化的 ES70二氧化硅， 加入 40ml 甲苯搅拌， 再加入 10ml TiCl4 ( 5v/v% TiCl4己烷溶液） ， 20Ό下反应 16hr。 用 20ml X 3甲苯洗涤、 过滤， 最后真空干燥得到修饰载体。 Preparation of modified carrier: 2 g of superheat-activated ES70 silica was weighed, stirred with 40 ml of toluene, and then added with 10 ml of TiCl 4 (5 v/v% TiCl 4 in hexane), and reacted at 20 Torr for 16 hr. It was washed with 20 ml of X 3 toluene, filtered, and finally vacuum dried to give a modified carrier.
复合载体的制备： 称取 2克无水氯化镁， 加入 40ml THF， 滴加 5ml 无水乙醇， 在 50°C下搅拌 2小时充分溶解后， 再加入 2g修饰载体， 50 Preparation of composite carrier: Weigh 2 g of anhydrous magnesium chloride, add 40 ml of THF, add 5 ml of absolute ethanol dropwise, stir at 50 ° C for 2 hours to fully dissolve, and then add 2 g of modified carrier, 50
°C下继续搅拌 4h， 将混合液用 20ml X 4 曱苯洗涤、 过滤， 最后真空干 燥，得到复合载体。氯化镁含水量应小于质量的 1 %，平均粒径为 30μιη; 比表面积为 25mVg。 复合载体的制备过程， 应在 50 °C搅拌条件下充分 反应形成透明体系。 时间为 4小时。 Stirring was continued for 4 h at ° C, the mixture was washed with 20 ml of X 4 benzene, filtered, and then vacuum dried to give a composite carrier. The water content of magnesium chloride should be less than 1% by mass, the average particle size is 30 μm, and the specific surface area is 25 mVg. The preparation process of the composite carrier should be fully reacted to form a transparent system under stirring at 50 °C. The time is 4 hours.
修饰复合载体的制备：加入 40ml甲苯到 4g复合载体中，滴加 4. 0ml 甲基铝氧烷 （10wt % MAO 甲苯溶液） 和 20mlTiCl4 ( 5v/v% TiCl4 己烷 溶液） ， 20Ό下搅拌反应 2 小时。 将混合液用 30ml 曱苯洗涤、 过滤、 真空干燥后得到修饰复合载体。 Preparation of the modified composite carrier: 40 ml of toluene was added to 4 g of the composite carrier, and 4. 0 ml of methylaluminoxane (10 wt% of MAO in toluene) and 20 ml of TiCl 4 (5 v/v% of TiCl 4 in hexane) were added dropwise, and stirred under 20 Torr. Reaction for 2 hours. The mixed solution was washed with 30 ml of toluene, filtered, and dried in vacuo to give a modified composite carrier.
负载型非茂金属催化剂的制备： 将 0. 120g结构式为  Preparation of supported non-metallocene catalyst: 0.1120g structural formula is
Figure imgf000031_0001
Figure imgf000031_0001
的非茂金属催化剂， 加入 1. 52ml四氢呋喃 （THF )溶剂， 加热到 50°C 完全溶解后， 加入 4g修饰复合载体， 充分搅拌 2小时后， 静置 12小 时后真空干燥得到负载型非茂金属催化剂。 The non-metallocene catalyst was added to a solvent of 1.52 ml of tetrahydrofuran (THF), heated to 50 ° C and completely dissolved. Then, 4 g of the modified composite carrier was added, and the mixture was stirred for 2 hours, then allowed to stand for 12 hours, and then vacuum dried to obtain a supported non-metallocene. catalyst.
由此所得到的复合载体、 修饰复合载体和负载型非茂金属催化剂 复制载体形态， 都是干的、 可流动的固体粉末。  The thus obtained composite carrier, modified composite carrier and supported non-metallocene catalyst replication carrier form are dry, flowable solid powders.
催化剂记为 CAT 1-1。  The catalyst was recorded as CAT 1-1.
采用 CAT 1-1的聚合过程为： 乙烯均聚合： 在 10L的高压聚合反应釜中同时加入 50mg负载型催 化剂、 5ml助催化剂曱基铝氧烷（MA0 )溶液（浓度为 10wt % ) 以及 5L 己烷溶剂， 开启搅拌速度为 250 rpm, 通入乙烯到聚合压力 2. 0MPa、 在 50°C下进行乙烯均聚。 经干燥得到 735g聚合物。 The polymerization process using CAT 1-1 is: Ethylene homopolymerization: 50 mg of supported catalyst, 5 ml of cocatalyst decyl aluminoxane (MA0) solution (concentration of 10 wt%) and 5 L of hexane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 250 rpm. Ethylene homopolymerization was carried out at 50 ° C under the polymerization pressure of 2.0 MPa. Drying gave 735 g of polymer.
聚合结果表明： 催化剂活性释放平稳， 乙烯消耗速率平稳， 催化 剂活性 14. 7 KgPE/g cat , 聚合物表观密度 0. 330g/cm3。 实施例 1-1-1， 与实施例 1-1基本相同， 但有如下改变： The polymerization results showed that the activity of the catalyst was stable, and the ethylene consumption rate was stable. The activity of the catalyst was 14.7 KgPE/g cat , and the apparent density of the polymer was 0.33 g/cm 3 . Embodiment 1-1-1 is basically the same as Embodiment 1-1, but with the following changes:
化学活化剂采用氟化钛；  The chemical activator uses titanium fluoride;
将热活化后的载体与氟化钛作用， 过滤洗涤干燥和抽干后得到修 饰载体。  The thermally activated support is reacted with titanium fluoride, filtered, washed and dried to obtain a modified carrier.
将氟化镆溶解于四氢呋喃-甲醇混合体系中形成溶液。  The cesium fluoride was dissolved in a tetrahydrofuran-methanol mixed system to form a solution.
催化剂记为 CAT 1-1-1。  The catalyst was recorded as CAT 1-1-1.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1- 2， 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Example 1-1- 2, which is basically the same as Example 1-1, but with the following changes:
二氧化硅采用 ES70X, 在氮气氛 500 下焙烧 8小时；  Silica was calcined with ES70X for 8 hours under a nitrogen atmosphere of 500;
化学活化剂采用溴化钛；  The chemical activator uses titanium bromide;
将活化后的载体与溴化钛作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with titanium bromide, filtered, washed and dried to obtain a modified carrier.
将碘化镁溶解于四氢呋喃 -丙醇混合体系中形成溶液。  The magnesium iodide is dissolved in a tetrahydrofuran-propanol mixed system to form a solution.
催化剂记为 CAT 1-1-2。  The catalyst was recorded as CAT 1-1-2.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1-3， 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Embodiments 1-1-3 are basically the same as Embodiment 1-1, but with the following changes:
二氧化硅釆用 Grace 948 , 在氩气氛 600Ό下焙烧 6小时； 化学活化剂采用碘化钛；  The silica crucible is calcined with Grace 948 under an argon atmosphere at 600 Torr for 6 hours; the chemical activator is titanium iodide;
将活化后的载体与碘化钛作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with titanium iodide, filtered, washed and dried to obtain a modified carrier.
将溴化镁溶解于四氢呋喃 -丁醇混合体系中形成溶液。  The magnesium bromide is dissolved in a tetrahydrofuran-butanol mixed system to form a solution.
催化剂记为 CAT 1-1-3。  The catalyst was recorded as CAT 1-1-3.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1-4， 与实施例 1-1基本相同， 但有如下改变： 二氧化硅采用 Grace SP9-485 , 在氮气氛 700°C下焙烧 5小时； 化学活化剂采用氯化锆； The polymerization process was the same as the polymerization process using CAT 1-1 in Example 1-1. Example 1-1-4, substantially the same as Example 1-1, but with the following changes: Silica using Grace SP9-485, calcined in a nitrogen atmosphere at 700 ° C for 5 hours; chemical activator using zirconium chloride;
将活化后的载体与氯化锆作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with zirconium chloride, filtered, washed and dried to obtain a modified carrier.
将氯化镁溶解于四氢呋喃 -戊醇混合体系中形成溶液。  Magnesium chloride is dissolved in a tetrahydrofuran-pentanol mixed system to form a solution.
催化剂记为 CAT 1-1- „  The catalyst is recorded as CAT 1-1- „
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1-5， 与实施例 I - 1基本相同， 但有如下改变： 二氧化硅采用 Grace SP9-10046 , 在氩气氛 800。C下焙烧 4小时； 化学活化剂采用氟化锆；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Examples 1-1-5 were substantially the same as in Examples I-1 except that the silica was used in Grace SP9-10046 in an argon atmosphere at 800. Calcined at C for 4 hours; the chemical activator is zirconium fluoride;
将活化后的载体与氟化锆作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with zirconium fluoride, filtered, washed and dried to obtain a modified carrier.
将氯化镁溶解于四氢呋喃 -己醇混合体系中形成溶液。  Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
催化剂记为 CAT 1-1-5。  The catalyst was recorded as CAT 1-1-5.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1- 6， 与实施例 1-1基本相同， 但有如下改变： 二氧化硅采用 EP10X, 在氮气氛 600Ό下焙烧 6小时；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Example 1-1-6, substantially the same as Example 1-1, but with the following changes: Silica was prepared by EP10X under a nitrogen atmosphere at 600 Torr for 6 hours;
化学活化剂采用溴化锆；  The chemical activator uses zirconium bromide;
将活化后的载体与溴化锆作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with zirconium bromide, filtered, washed and dried to obtain a modified carrier.
将氯化镁溶解于四氢呋喃 -己醇混合体系中形成溶液。  Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
催化剂记为 CAT I-l-60 Catalyst is recorded as CAT Il-6 0
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1- 7， 与实施例 1-1基本相同， 但有如下改变： 二氧化硅采用 CS-2133 , 在氮气氛 300 'C下焙烧 18小时； 化学活化剂采用碘化牿；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Example 1-1-7, which is basically the same as Example 1-1, but with the following changes: Silica is CS-2133, calcined in a nitrogen atmosphere at 300 ° C for 18 hours; chemical activator is cesium iodide;
将活化后的载体与碘化锆作用， 过滤洗涤干燥和抽干后得到修饰 载体。 将氯化镁溶解于四氢呋喃 -己醇混合体系中形成溶液。 The activated carrier is reacted with zirconium iodide, filtered, washed and dried to obtain a modified carrier. Magnesium chloride is dissolved in a tetrahydrofuran-hexanol mixed system to form a solution.
催化剂记为 CAT 1-1-7。  The catalyst was recorded as CAT 1-1-7.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1- 8 , 与实施例 1-1基本相同， 但有如下改变： 二氧化硅采用 MS- 3040， 在氮气氛 1000Ό下焙烧 1小时； 化学活化剂采用氯化铝；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Examples 1-1-8, which are basically the same as those of Example 1-1, but have the following changes: Silica is MS- 3040, calcined under a nitrogen atmosphere at 1000 Torr for 1 hour; chemical activator is aluminum chloride;
将活化后的载体与氯化铝作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with aluminum chloride, filtered, washed and dried to obtain a modified carrier.
将氯化镁溶解于四氢呋喃 -庚醇混合体系中形成溶液。  Magnesium chloride is dissolved in a tetrahydrofuran-heptanol mixed system to form a solution.
催化剂记为 CAT 1-1-8。  The catalyst was recorded as CAT 1-1-8.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1- 9， 与实施例 1-1基本相同， 但有如下改变： 二氧化硅采用中空二氧化硅， 在氮气氛 100TC下干燥 24小时； 化学活化剂采用溴化铝；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Examples 1 to 9 were substantially the same as those of Example 1-1 except that the silica was hollow silica, dried under a nitrogen atmosphere at 100 TC for 24 hours; and the chemical activator was aluminum bromide;
将活化后的载体与溴化铝作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with aluminum bromide, filtered, washed and dried to obtain a modified carrier.
将氯化镁溶解于四氢呋喃 -乙醇混合体系中形成溶液。  Magnesium chloride was dissolved in a tetrahydrofuran-ethanol mixed system to form a solution.
催化剂记为 CAT 1-1-9 D Catalyst is recorded as CAT 1-1-9 D
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-1- 10, 与实施例 1-1基本相同， 但有如下改变： 化学活化剂采用碘化铝；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Examples 1-1-10, substantially the same as Example 1-1, but with the following changes: The chemical activator is aluminum iodide;
将活化后的载体与碘化铝作用， 过滤洗涤干燥和抽干后得到修饰 载体。  The activated carrier is reacted with aluminum iodide, filtered, washed and dried to obtain a modified carrier.
将氯化镁溶解于四氢呋喃 -乙醇混合体系中形成溶液。  Magnesium chloride was dissolved in a tetrahydrofuran-ethanol mixed system to form a solution.
催化剂记为 CAT 1-1-10。  The catalyst was recorded as CAT 1-1-10.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-2， 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Embodiment 1-2 is basically the same as Embodiment 1-1, but with the following changes:
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000035_0001
The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000035_0001
载体二氧化硅的热活化条件是： 600Ό、 氮气氛下焙烧 6h; 氯化镆与二氧化硅的质量比为 1 : 0. 1 ;  The thermal activation condition of the carrier silica is: 600 Torr, calcined for 6 h under a nitrogen atmosphere; mass ratio of lanthanum chloride to silica is 1:0.
化学活化剂采用四氯化钛；  The chemical activator uses titanium tetrachloride;
经过热活化的二氧化硅与四氯化钛的己烷溶液反应 4 小时后, 滤， 己烷洗涤三次并干燥得到修饰载体。  After heat-activated silica was reacted with a solution of titanium tetrachloride in hexane for 4 hours, it was filtered, washed three times with hexane and dried to give a modified carrier.
干燥后的修饰二氧化硅载体是干的可流动的粉末。  The dried modified silica support is a dry flowable powder.
催化剂记为 CAT 1-2。  The catalyst was recorded as CAT 1-2.
四氢呋喃 -醇混合体系改为四氢呋喃 -环己醇；  The tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclohexanol;
其中溶解的镁化合物改为 MgC10CH3; The dissolved magnesium compound is changed to MgC10CH 3 ;
对复合载体进行化学修饰的修饰剂改为三乙基铝。 实施例 1-2-1， 与实施例 1-2基本相同， 但有如下改变： 四氢呋喃一醇混合体系改为四氢呋喃一环戊醇；  The modifier which chemically modified the composite carrier was changed to triethylaluminum. Example 1-2-1, which is basically the same as Example 1-2, but with the following changes: The tetrahydrofuran-ol mixed system is changed to tetrahydrofuran-cyclopentanol;
镁化合物改为 MgC10CH2CH3; The magnesium compound was changed to MgC10CH 2 CH 3 ;
对复合载体进行化学修饰的修饰剂改为三甲基铝。  The modifier which chemically modified the composite carrier was changed to trimethylaluminum.
催化剂改为具有以下结构式的化合物：  The catalyst was changed to a compound having the following structural formula:
Figure imgf000035_0002
Figure imgf000035_0002
催化剂记为 CAT 1-2-1。  The catalyst was recorded as CAT 1-2-1.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-2- 2 , 与实施例 1-2基本相同， 但有如下改变： 四氢呋喃 -醇混合体系改为四氢呋喃 -环辛醇；  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Example 1-2- 2 , substantially the same as Example 1-2, but with the following changes: The tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclooctyl alcohol;
镁化合物改为 MgC10C4H9； The magnesium compound was changed to M g C10C 4 H 9 ;
对复合载体进行化学修饰的修饰剂改为三异丁基铝。  The modifier which chemically modified the composite carrier was changed to triisobutylaluminum.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000036_0001
The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000036_0001
催化剂记为 CAT 1-2-2。 The catalyst was recorded as CAT 1-2-2.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-2-3， 与实施例 1-2基本相同， 但有如下改变： 镁化合物改为 MgBrOCH3; The polymerization process was the same as the polymerization process using CAT 1-1 in Example 1-1. Example 1-2-3 was substantially the same as Example 1-2 except that the magnesium compound was changed to MgBrOCH 3 ;
催化剂改为具有以下结构式的化合物：  The catalyst was changed to a compound having the following structural formula:
Figure imgf000036_0002
Figure imgf000036_0002
催化剂记为 CAT 1-2-3。 The catalyst was recorded as CAT 1-2-3.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-2-4， 与实施例 1-2基本相同， 但有如下改变： 镁化合物改为 MgBrOCH2CH3。 The polymerization process was the same as the polymerization process using CAT 1-1 in Example 1-1. Example 1-2-4 was substantially the same as Example 1-2 except that the magnesium compound was changed to MgBrOCH 2 CH 3 .
合催化剂改为具有以下结构式的化合物:
Figure imgf000036_0003
The catalyst is changed to a compound having the following structural formula:
Figure imgf000036_0003
催化剂记为 CAT 1-2-4„ The catalyst is recorded as CAT 1-2-4
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-2 - 5， 与实施例 1-2基本相同， 但有如下改变： 镁化合物改为 MgBrOC4H9。 The polymerization process was the same as the polymerization process using CAT 1-1 in Example 1-1. Examples 1-2 - 5 were substantially the same as those of Example 1-2 except that the magnesium compound was changed to M g BrOC 4 H 9 .
化剂改为具有以下结构式的化合物：  The chemical is changed to a compound having the following structural formula:
Figure imgf000036_0004
催化剂记为 CAT 1-2-5。
Figure imgf000036_0004
The catalyst was recorded as CAT 1-2-5.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-3， 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Embodiments 1-3 are basically the same as Embodiment 1-1, but with the following changes:
载体二氧化硅的热活化条件是： 氩气氛下干燥或焙烧 8小时; 氯化镁与二氧化硅的质量比为 1 ： 10。  The thermal activation conditions of the supported silica are: drying or calcination under an argon atmosphere for 8 hours; mass ratio of magnesium chloride to silica is 1:10.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000037_0001
Figure imgf000037_0001
催化剂记为 CAT 1-3。  The catalyst was recorded as CAT 1-3.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-4 , 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Embodiments 1-4 are basically the same as Embodiment 1-1, but with the following changes:
二氧化硅不进行热活化， 直接与氯化镁作用得到复合载体;  Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier;
镁与二氧化硅的质量比为 1 ： 1。 The mass ratio of magnesium to silica is 1:1.
烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000037_0002
The hydrocarbon polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000037_0002
催化剂记为 CAT 1-4。  The catalyst was recorded as CAT 1-4.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-5 , 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Embodiments 1-5 are basically the same as Embodiment 1-1, but with the following changes:
复合载体直接与非茂金属烯烃聚合催化剂反应， 不与化学处理剂 作用， 不需制成修饰复合载体。  The composite carrier is directly reacted with the non-metallocene olefin polymerization catalyst, does not react with the chemical treatment agent, and does not need to be a modified composite carrier.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000037_0003
催化剂记为 CAT 1-5。
Figure imgf000037_0003
The catalyst was recorded as CAT 1-5.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-6 , 与实施例 1-1基本相同， 但同时有如下两个改变： 二氧化硅不进行热活化， 直接与氯化镁作用得到复合载体； 氯化 镁与二氧化硅的质量比为 1 : 1;  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Example 1-6, which is basically the same as Example 1-1, but has the following two changes: Silica is not thermally activated, and directly reacts with magnesium chloride to obtain a composite carrier; the mass ratio of magnesium chloride to silica is 1: 1;
复合载体直接与非茂金属烯烃聚合催化剂反应， 不与化学处理剂 作用， 不需制成修饰复合载体。  The composite carrier is directly reacted with the non-metallocene olefin polymerization catalyst, does not react with the chemical treatment agent, and does not need to be a modified composite carrier.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000038_0001
The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000038_0001
催化剂记为 CAT 1-6。  The catalyst was recorded as CAT 1-6.
聚合过程与实施例 1-1中采用 CAT 1-1的聚合过程相同。 实施例 1-7 , 与实施例 1-1基本相同， 但有如下改变：  The polymerization process was the same as that in Example 1-1 using CAT 1-1. Embodiments 1-7 are basically the same as Embodiment 1-1, but with the following changes:
载体采用氧化镁。  The carrier uses magnesium oxide.
改为具有以下结构式的化合物：  Change to a compound with the following structural formula:
Figure imgf000038_0002
Figure imgf000038_0002
催化剂记为 CAT 1-7。 The catalyst was recorded as CAT 1-7.
实施例 I- 1 - 1-7聚合效果一览表 Example I-1 - 1-7 Polymerization Effect List
(采用 10升聚合反应釜进行乙烯均聚， 聚合压力 2. 0MPa、 聚合温度为 50'C , 聚合 (Using a 10 liter polymerization reactor for ethylene homopolymerization, polymerization pressure 2. 0 MPa, polymerization temperature 50'C, polymerization
Figure imgf000039_0001
Figure imgf000039_0001
负载型非茂金属烯烃聚合催化剂在烯烃聚合和共聚中应用的实施例 在以下实施例中， 制备了本发明的负载型非茂金属烯烃聚合催化 剂， 并将其用于烯烃的聚合和共聚中。 参照例 2-1 Examples of Application of Supported Non-metallocene Olefin Polymerization Catalysts in Olefin Polymerization and Copolymerization In the following examples, the supported non-metallocene olefin polymerization catalysts of the present invention were prepared. And used in the polymerization and copolymerization of olefins. Reference example 2-1
负载型催化剂的制备： 取 ES70型二氧化硅（Crosfield公司产品） 在氮气气氛 650TC下恒温 6h流化活化。 将分析纯氯化镁在 500°C下煅烧 3h制得无水氯化镆。 在氮气氛下 （水和氧的含量均低于 5ppm ) ， 称取 3 克无水氯化镁， 加入 60ml精制四氢呋喃 ( THF ) ， 然后滴加 2. 5ml精制 无水乙醇， 再加入 3g热活化的 ES70载体， 20Ό下搅拌反应 18h, 将混 合液用 30ml X 4曱苯洗涤、过滤，最后真空干燥，得 5g复合载体。将 50ml 甲苯加入到复合载体中， 滴加 5ml曱基铝氧烷 ( 10wt %MA0甲苯溶液） 和 25mlTiCl4 ( 5v/v% TiCl4己烷溶液） , 20X下搅拌反应 16小时。 将混 合液用 30ml X 4甲苯洗涤、 过滤， 最后真空干燥， 再加入 0. 5g结构式为 Preparation of supported catalyst: ES70 type silica (Crosfield product) was fluidized and activated at a constant temperature of 6 h under a nitrogen atmosphere of 650 TC. The analytical pure magnesium chloride was calcined at 500 ° C for 3 h to obtain anhydrous cesium chloride. Under a nitrogen atmosphere (water and oxygen content are less than 5 pp m ), weigh 3 g of anhydrous magnesium chloride, add 60 ml of refined tetrahydrofuran (THF), then add 2.5 ml of refined anhydrous ethanol, and then add 3 g of heat activated The ES70 carrier was stirred for 18 hours at 20 ° C. The mixture was washed with 30 ml of X 4 benzene, filtered, and then dried in vacuo to give 5 g. 50 ml of toluene was added to the composite carrier, and 5 ml of mercaptoaluminoxane (10 wt% MA0 in toluene solution) and 25 ml of TiCl 4 (5 v/v% TiCl 4 in hexane solution) were added dropwise, and the reaction was stirred at 20X for 16 hours. 5克结构为为。 The structure of the structure is 0. 5g
Figure imgf000040_0001
的非茂金属催化剂的 20ml甲苯的溶液， 20°C下搅拌反应 6小时， 溶液再 用 30ml X 4甲苯洗涤、 过滤， 最后真空干燥， 得到催化剂前体 4. 5g, 与 1. 12g上述结构的非茂金属催化剂的 THF溶液进行等体积浸渍， 最后真 空干燥得到负载型非茂金属催化剂， 催化剂记为 CAT1。 实施例 2-1
Figure imgf000040_0001
5g,与1. 12g的结构的的的的的的的的的的的的的的的的的的的的的的的的The non-metallocene catalyst in THF was subjected to an equal volume impregnation, and finally vacuum dried to obtain a supported non-metallocene catalyst, and the catalyst was designated as CAT1. Example 2-1
负载型催化剂的制备： 称取 2g参照例 2-1中热活化的 ES70二氧化 硅， 加入 40ml曱苯搅拌， 再加入 10ml TiCl4 ( 5v/v% TiCl4己烷溶液） ， 20Ό下反应 16hr。 用 20ml χ 3甲苯洗涤、 过滤， 最后真空干燥。 称取 2 克无水氯化镁， 加入 40ml THF, 滴加 5ml无水乙醇， 再加入前述载体， 50°C下搅拌 4h， 将混合液用 20ml X 4甲苯洗涤、 过滤， 最后真空干燥， 得 2. 9g复合载体。 加入 40ml曱苯到复合载体中， 滴加 2. 9ml曱基铝氧 烷（15wt %MA0甲苯溶液）和 15mlTiCl4 ( 5v/v% TiCl4己烷溶液） ， 20 下搅拌反应 2小时。 将混合液用 30ml曱苯洗涤、 过滤、 真空干燥后， 再 加入 0. 256g非茂金属催化剂的甲苯溶液， .20 下搅拌反应 16小时， 混 合液再用 30ml x 3曱苯洗涤、 过滤、 真空千燥， 得到催化剂前体。 称取 催化剂前体 0. 5g , 加入 0· 125g非茂金属催化剂的 THF饱和溶液进行等 体积浸渍， 并充分搅拌均匀， 真空干燥得到负载型非茂金属催化剂， 催 化剂记为 CAT2。 实施例 2-2 Preparation of supported catalyst: 2 g of heat-activated ES70 silica in Reference Example 2-1 was weighed, stirred with 40 ml of toluene, and then added with 10 ml of TiCl 4 (5 v/v% TiCl 4 in hexane) and reacted at 20 Torr for 16 hr. . It was washed with 20 ml of hydrazine 3 toluene, filtered, and finally dried under vacuum. Weigh 2 g of anhydrous magnesium chloride, add 40 ml of THF, add 5 ml of absolute ethanol, add the above carrier, stir at 50 ° C for 4 h, wash the mixture with 20 ml of X 4 toluene, filter, and finally vacuum dry, to obtain 2. 9g composite carrier. Yue 40ml benzene was added to the composite carrier was added dropwise 2. 9ml Yue of methyl aluminoxane (15wt% MA0 toluene solution) and 15mlTiCl 4 (5v / v% TiCl 4 in hexane), stirred for 2 hours at 20. The mixture was washed with 30 ml of hydrazine, filtered, and dried in vacuo. Then, 256 g of a non-metallocene catalyst in toluene was added, and the reaction was stirred for 16 hours at .20, mixed. The combined liquid was washed with 30 ml of x 3 benzene, filtered, and vacuum dried to obtain a catalyst precursor. The catalyst precursor was weighed 0.5 g, and an isocratic immersion solution of 0·125 g of a non-metallocene catalyst was added thereto, and uniformly stirred, and uniformly dried, and vacuum-dried to obtain a supported non-metallocene catalyst, and the catalyst was recorded as CAT2. Example 2-2
乙烯均聚合： 在 10L的间歇式聚合反应釜中同时加入 46mg负载型催 化剂 CAT2、 8ml MAO溶液（浓度为 15wt % ) 以及 5L己烷溶剂 , 开启搅拌 速度为 250 rpm, 通入乙烯到聚合压力 2. 0MPa、 在 下进行乙烯均聚， 反应时间为 3h。 实施例 2-3  Ethylene homopolymerization: Simultaneously add 46 mg of supported catalyst CAT2, 8 ml of MAO solution (concentration of 15 wt%) and 5 L of hexane solvent in a 10 L batch polymerization reactor, and start stirring at 250 rpm, and pass ethylene to polymerization pressure 2 0 MPa, ethylene homopolymerization was carried out, and the reaction time was 3 h. Example 2-3
乙烯氢调聚合： 往 2L高压釜中同时加入 31. 2mg负载型催化剂 CAT2、 3. lml MAO的甲苯溶液（浓度为 15wt % )以及 1L己烷，搅拌速度为 500rpm, 维持聚合压力 2· 0MPa， 其中氢气压力 0. 1MPa、 在 50Ό进行氢调下乙烯 均聚合， 反应时间为 2h。 实施例 2-4  Ethylene hydrogenation polymerization: To a 2L autoclave, 31.2 mg of supported catalyst CAT2, 3. lml of MAO in toluene solution (concentration of 15 wt%) and 1 L of hexane were added, the stirring speed was 500 rpm, and the polymerization pressure was maintained at 2.0 MPa. The hydrogen pressure was 0.1 MPa, and the ethylene polymerization was carried out under hydrogenation at 50 Torr. The reaction time was 2 h. Example 2-4
乙丙氢调共聚合：往 10L高压釜中同时加入 40mg负载型催化剂 CAT2、 9ml MAO的甲苯溶液（浓度为 15wt % )以及 5L己烷， 搅拌速度为 250rpm, 聚合压力 2. OMPa , 其中氢气压力 0. 15MPa。 通入乙烯 7分钟后用计量泵 加入丙烯单体 65g, 47分钟后再加入丙烯 80g， 90分钟后再次加入丙烯 75g, 在 50°C下进行乙烯与丙烯共聚合， 反应时间为 3h。 实施例 2 - 5  IMPa, Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. Hydrogen pressure. 0. 15MPa. After 7 minutes of ethylene feeding, 65 g of propylene monomer was added by a metering pump, and after 80 minutes, 80 g of propylene was further added. After 90 minutes, 75 g of propylene was again added, and ethylene and propylene were copolymerized at 50 ° C for 3 hours. Example 2 - 5
乙丁共聚合：往 2L高压釜中同时加入 19. 5mg负载型催化剂 CAT2、 2ml MA0的甲苯溶液（浓度为 15wt % ) 以及 1L己垸， 搅拌速度为 500rpm， 聚 合压力 2. OMPa , 通入乙烯 5分钟后加入丁烯- 1 40g, 在 50Ό下进行乙烯 与 1-丁烯共聚合， 反应时间为 2h。 实施例 2-6  The propylene is fed into the ethylene. The polymerization is carried out at a pressure of 500 rpm. The polymerization pressure is 2.0 MPa. After 5 minutes, butene-1 40 g was added, and ethylene and 1-butene were copolymerized at 50 Torr for 2 hours. Example 2-6
氢调乙丁共聚合： 往 2L高压釜中同时加入 25mg负载型催化剂 CAT2、 2. 5ml MAO的曱苯溶液（浓度为 15wt % )以及 1L己烷，搅拌速度为 500rpm， 聚合压力 2. 0MPa, 其中氢气压力为 0· lMPa。 通入乙烯 5分钟后加入丁 烯单体 50g, 在 50Ό下进行乙烯与 1-丁烯共聚合反应， 反应时间为 。 实施例 2-7 Hydrogen-terminated Ethylene Co-polymerization: Add 25 mg of supported catalyst CAT2 to a 2 L autoclave simultaneously 2MPa。 The hydrogen peroxide pressure is 0·lMPa. The polymerization pressure is 2.0 MPa, and the hydrogen pressure is 0·1 MPa. Five minutes after the introduction of ethylene, 50 g of butene monomer was added, and ethylene and 1-butene were copolymerized at 50 Torr for the reaction time. Example 2-7
乙己共聚合： 往 2L高压釜中同时加入 16. 3mg负载型催化剂 CAT2、 1. 6ml MAO的甲苯溶液（浓度为 15wt % )以及 1L己烷，搅拌速度为 500rpm, 聚合压力 2. 0MPa， 通入乙烯 5分钟后加入 1-己烯 30g， 在 50°C下进行 乙烯与 1-己烯共聚合反应， 反应时间为 2h。 实施例 2-8  The singularity of the polymerization is 2. MPa, the polymerization is carried out at a pressure of 500 rpm, the stirring pressure is 500 rpm, and the polymerization pressure is 2.0 MPa. After 5 minutes of ethylene, 30 g of 1-hexene was added, and ethylene and 1-hexene were copolymerized at 50 ° C for 2 hours. Example 2-8
氢调乙己共聚合： 往 2L高压釜中同时加入 32mg负载型催化剂 CAT2、 Hydrogen-terminated ethylene co-polymerization: Add 32mg of supported catalyst CAT2 to 2L autoclave simultaneously
3. 2ml MAO的甲苯溶液（浓度为 15wt % ) 以及 1L己烷溶剂， 搅拌速度为 500rpm, 聚合压力 2· OMPa, 其中氢气压力为 0. 19MPa, 通入乙烯 5分钟 后加入 1-己烯 50g,在 50°C下进行乙烯与 1-己烯共聚合，反应时间为 2h。 实施例 2-9 3. 2 ml of MAO in toluene solution (concentration of 15 wt%) and 1 L of hexane solvent, stirring speed of 500 rpm, polymerization pressure of 2·OMPa, wherein hydrogen pressure is 0. 19MPa, after adding ethylene for 5 minutes, adding 1-hexene 50g The copolymerization of ethylene and 1-hexene was carried out at 50 ° C for a reaction time of 2 h. Example 2-9
负载型催化剂的制备： 取 5g按照参照例 2-1热活化的 ES70二氧化 硅， 加入 25ml己烷和 25ml TiCl4 ( 5v/v% TiCl4己烷溶液） , 35 Ό下搅 拌反应 5小时， 用 30ml X 3己烷洗涤、 过滤、 真空干燥。 按照实施例 2- 1负载型催化剂制备方法制^ ^化剂 CAT3。 实施例 2 - 10 Preparation of supported catalyst: 5 g of ES70 silica thermally activated according to Reference Example 2-1 was taken, 25 ml of hexane and 25 ml of TiCl 4 (5 v/v% TiCl 4 in hexane solution) were added, and the reaction was stirred for 5 hours under 35 Torr. Wash with 30 ml of X 3 hexane, filter and dry in vacuo. The catalyst CAT3 was prepared according to the procedure of Example 2-1-2 supported catalyst preparation. Example 2 - 10
乙烯均聚合：在 2L高压釜中同时加入 26mg负载型催化剂 CAT3、2. 6ml MA0的曱苯溶液（浓度为 l Owt % )以及 1L己烷，开启搅拌速度为 500rpm， 通入乙烯到聚合压力 2. 0MPa 在 50Ό下进行乙烯均聚， 反应时间为 2h。 实施例 2 - 11  Ethylene homopolymerization: In a 2L autoclave, 26 mg of supported catalyst CAT3, 2.6 ml of MA0 in benzene solution (concentration of 10 wt%) and 1 L of hexane were added simultaneously, the stirring speed was 500 rpm, and ethylene was fed to the polymerization pressure 2 0MPa Ethylene homopolymerization was carried out at 50 Torr for a reaction time of 2 h. Example 2 - 11
乙烯均聚：在 2L聚合反应釜中加入 100ml的聚乙烯粉末，再加入 20mg 的 CAT3催化剂和 2ml的 MA0甲苯溶液， 在 60Π， 500rpm下搅拌反应 , 皮应压力为 2. OMPa, 反应时间为 2hr。 实施例 2-12 OMPa,反应时间为2hr, the reaction time is 2 hr, the reaction time is 2 hr, the reaction time is 2 hr, the reaction time is 2 hr, the reaction time is 2 hr, the reaction time is 2 hr, and the reaction time is 2 hr. . Example 2-12
乙烯均聚： 在 2L高压釜中同时加入 21. 5mg负载型催化剂 CAT3、 ½1 TEA的己烷溶液（0. 5M)以及 1L己烷， 开启搅拌速度为 500rpm, 通入乙烯 到聚合压力 2. 0MPa、 在 501C下进行乙烯均聚， 反应时间为 2hr。 实施例 2-13  0MPa。 The ethylene was homopolymerized to a polymerization pressure of 2. 0MPa. The propylene was added to a polymerization pressure of 2. 0MPa. Ethylene homopolymerization was carried out at 501 C for a reaction time of 2 hr. Example 2-13
乙烯均聚：在 2L高压釜中同时加入 16. Omg负载型催化剂 CAT3、3. 2ml TiBA的己烷溶液（15wt°/。）以及 1L己垸， 开启搅拌速度为 250rpm， 通入乙 烯到聚合压力 2. 0MPa、 在 70Ό下进行乙烯均聚， 反应时间为 2hr。 实施例 2-14  Ethylene homopolymerization: In a 2 L autoclave, 16. Omg of supported catalyst CAT3, 3.2 ml of TiBA in hexane solution (15 wt% /.) and 1 L of hexane were added, and the stirring speed was 250 rpm, and ethylene was fed to the polymerization pressure. 2. 0 MPa, ethylene homopolymerization at 70 Torr, reaction time 2 hr. Example 2-14
乙丙共聚合：往 2L高压釜中同时加入 18mg负载型催化剂 CAT3、 1. 8ml MAO的曱苯溶液（浓度为 15wt % ) 以及 1L己烷， 搅拌速度为 500rpni, 聚 合压力 2. 0MPa， 通入乙烯 13min后加入丙烯单体 40 g , 在 5 (TC下进行乙 烯与丙烯共聚合， 反应时间为 2h。 实施例 2-15  The propylene, the polymerization pressure is 2.0 MPa, and the polymerization is carried out at a pressure of 500 rpni, a polymerization pressure of 2.0 MPa, and a polymerization rate of 2.0 MPa. After 13 minutes of ethylene, 40 g of propylene monomer was added, and ethylene and propylene were copolymerized at 5 (TC) for 2 h. Example 2-15
氢调乙烯均聚 ： 将 600mg负载型催化剂 CAT3、 60ml MAO的甲苯溶 液（浓度为 10wt % ) 以及 5L己烷一起加入到 4L预^^中， 在 500rpai 下进行催化剂体系预络合， 然后连同 80L己烷， 一起加入到 175L反应釜 中进行淤浆聚合， 搅拌速度为 400rpm， 聚合压力 2. 0MPa , 其中氢气压力 为 0. 25MPa， 在 65 °C下进行乙烯聚合， 反应时间为 2h。 终止反应。 实施例 2-16  Hydrogen-terminated ethylene homopolymerization: 600 mg of supported catalyst CAT3, 60 ml of MAO in toluene solution (concentration of 10 wt%) and 5 L of hexane were added together to 4 L of pre-compound, and the catalyst system was pre-complexed at 500 rpai, and then together with 80 L. The hexane was added to a 175 L reactor for slurry polymerization at a stirring speed of 400 rpm, a polymerization pressure of 2.0 MPa, wherein the hydrogen pressure was 0.25 MPa, and ethylene polymerization was carried out at 65 ° C for a reaction time of 2 h. Stop the reaction. Example 2-16
乙烯均聚： 在 2L高压釜中同时加入 18. 8mg负载型催化剂 CAT3 , 按 硼钛摩尔比 100加入三丁基铵四 （五氟硼）基硼以及 1L己烷， 开启搅拌 速度为 500rpm， 通入乙烯到聚合压力 2· 0MPa、 在 50°C下进行乙烯均聚， 反应时间为 2hr。 终止反应。 实施例 2-17  Ethylene homopolymerization: 18.8 mg of supported catalyst CAT3 was added simultaneously in a 2 L autoclave, and tributylammonium tetrakis(pentafluoroboron)boron and 1 L of hexane were added in a molar ratio of boron to titanium, and the stirring speed was 500 rpm. Ethylene was homopolymerized at a polymerization pressure of 2.0 MPa at 50 ° C for a reaction time of 2 hr. Stop the reaction. Example 2-17
乙辛共聚合： 往 2L高压釜中同时加入 20. 2mg负载型催化剂 CAT3、 2. 0ml MA0的甲苯溶液（浓度为 10wt % )以及 1L己烷，搅拌速度为 300rpm, 聚合压力 2. 0MPa， 通入乙烯 13min后加入 1-辛烯单体 40 g, 在 50°C下 进行乙烯与辛烯共聚合， 反应时间为 2h。 终止反应。 实施例 2 - 18 Ethylene copolymerization: 20.2 mg of supported catalyst CAT3, 2. 0 ml of MA0 in toluene solution (concentration of 10 wt%) and 1 L of hexane were added to a 2 L autoclave at a stirring speed of 300 rpm. The polymerization pressure was 2.0 MPa. After 13 minutes of ethylene addition, 40 g of 1-octene monomer was added, and ethylene and octene were copolymerized at 50 ° C for 2 h. Stop the reaction. Example 2 - 18
乙辛共聚合： 往 2L高压釜中同时加入 21. 8mg负载型催化剂 CAT3、 2. 2ml MAO的甲苯溶液（浓度为 10wt % )以及 1L己烷，搅拌速度为 300rpm, 聚合压力 2. 0MPa， 通入乙烯 13min后加入降水片烯单体 55 g, 在 50Ό下 进行乙烯与降水片烯共聚合， 反应时间为 2h。 终止反应。 在以下实施例中， 进一步制备了本发明的负载型非茂金属烯烃聚 合催化剂， 并将其用于烯烃的聚合和共聚中。 实施例 Π-1  0MPa,通。 The propylene, the propylene, the propylene, the propylene, the propylene, the propylene, the propylene, the propylene, the propylene, the propylene, the propylene After 13 minutes of ethylene addition, 55 g of precipitation monomer was added, and ethylene and precipitation olefin were copolymerized at 50 Torr for 2 hours. Stop the reaction. In the following examples, the supported non-metallocene olefin polymerization catalyst of the present invention was further prepared and used in the polymerization and copolymerization of olefins. Example Π-1
与实施例 1-1基本相同， 但有如下改变：  It is basically the same as Embodiment 1-1, but with the following changes:
二氧化硅改为 ES757。  The silica was changed to ES757.
催化剂记为 CAT Π -1。  The catalyst was recorded as CAT Π -1.
( 1 )采用 CAT Π - 1催化剂的聚合过程 1  (1) Polymerization process using CAT Π - 1 catalyst 1
乙烯均聚合： 在 10L的高压聚合反应釜中同时加入 50mg负载型催 化剂、 5ml 助催化剂三乙基铝 ( TEA )溶液（浓度为 15wt % ) 以及 5L 己烷溶剂， 开启搅拌速度为 250 rpm, 通入乙烯到聚合压力 2. OMPa ., 在 50Ό下进行乙烯均聚。 经干燥得到 770g聚合物。  Ethylene homopolymerization: 50 mg supported catalyst, 5 ml cocatalyst triethylaluminum (TEA) solution (concentration: 15 wt%) and 5 L of hexane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 250 rpm. Ethylene was homopolymerized at a polymerization pressure of 2. OMPa. After drying, 770 g of a polymer was obtained.
( 2 ) 采用 CAT Π -1催化剂的聚合过程 2  ( 2 ) Polymerization process using CAT Π -1 catalyst 2
氢调下乙烯均聚合： 在 10L 的高压聚合反应釜中同时加入 250mg 负载型催化剂、 250ml助催化剂甲基铝氧烷（MA0 )溶液（浓度为 10wt Ethylene homopolymerization under hydrogen adjustment: 250mg supported catalyst, 250ml cocatalyst methylaluminoxane (MA0) solution (concentration 10wt) simultaneously in a 10L high pressure polymerization reactor
% ) 以及 5L甲苯溶剂， 开启搅拌速度为 400 rpm, 加入氢气到 0· 3MPa , 然后通入乙烯到聚合压力 0. 8MPa、 在 ΙΟΟΌ下进行氢调下乙烯均聚合。 经干燥得到 1425g聚合物。 %) and 5 L of toluene solvent, the stirring speed was 400 rpm, hydrogen was added to 0. 3 MPa, and then ethylene was introduced to a polymerization pressure of 0.8 MPa, and ethylene was homopolymerized under hydrogen pressure. After drying, 1425 g of a polymer was obtained.
( 3 ) 采用 CAT Π -1催化剂的聚合过程 3  (3) Polymerization process using CAT Π -1 catalyst 3
乙烯和丁烯共聚合： 在 10L的高压聚合反应釜中同时加入 40mg负 载型催化剂、 28ml 助催化剂三乙基铝 ( TEA )溶液（浓度为 15wt % ) 以及 5L 癸烷溶剂， 开启搅拌速度为 400 rpm, 加入氢气到 0. 3MPa， 然后通入乙烯到聚合压力 0. 2MPa、 5分钟后泵如 40g丁烯， 在 80Ό下 进行乙烯和丁烯共聚合。 经干燥得到 520g聚合物。 Copolymerization of ethylene and butene: 40 mg of supported catalyst, 28 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of decane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 400. 5MPa, rpm, adding hydrogen to 0. 3MPa, Then, ethylene was introduced to a polymerization pressure of 0.2 MPa, and after 5 minutes, a pump such as 40 g of butene was subjected to copolymerization of ethylene and butene at 80 Torr. 5 2 0g dried to obtain a polymer.
( 4 )采用 CAT Π -1催化剂的聚合过程 4  (4) Polymerization process using CAT Π -1 catalyst 4
乙烯和己烯共聚合： 在 10L的高压聚合反应釜中同时加入 20ing负 载型催化剂、 25ml 助催化剂三异丁基铝 （IBAL )溶液（浓度为 15wt % ) 以及 5L辛烷溶剂， 开启搅拌速度为 400 rpm, 加入氢气到 0. 3MPa , 然后通入乙烯到聚合压力 0. 85MPa、 5分钟后泵入 20g 己烯， 在 60°C 下进行乙烯和己烯共聚合。 经干燥得到 92g聚合物。  Copolymerization of ethylene and hexene: 20 liters of supported catalyst, 25 ml of cocatalyst triisobutylaluminum (IBAL) solution (concentration of 15 wt%) and 5 L of octane solvent were added to a 10 L high pressure polymerization reactor, and the stirring speed was 400. After rpm, hydrogen was added to 0.3 MPa, and then ethylene was introduced to a polymerization pressure of 0.85 MPa. After 5 minutes, 20 g of hexene was pumped, and ethylene and hexene copolymerization was carried out at 60 °C. After drying, 92 g of a polymer was obtained.
( 5 )采用 CAT Π -1催化剂的聚合过程 5  (5) Polymerization process using CAT Π -1 catalyst 5
乙烯和降水片烯共聚合： 在 10L 的高压聚合反应釜中同时加入 120mg 负载型催化剂、 24ml 助催化剂乙基铝氧烷（ EA0 )溶液（浓度 为 15wt % ) 以及 5L 乙苯溶剂， 开启搅拌速度为 100 rpm, 然后通入 乙烯到聚合压力 0. 60MPa、 5分钟后泵入 30g降冰片烯， 在 1201：下进 行乙烯与降冰片烯共聚。 经干燥得到 888g聚合物。  Copolymerization of ethylene and precipitation olefin: In a 10L high pressure polymerization reactor, 120mg of supported catalyst, 24ml of cocatalyst ethylaluminoxane (EA0) solution (concentration of 15wt%) and 5L of ethylbenzene solvent were added simultaneously to open the stirring speed. After 100 rpm, ethylene was introduced to a polymerization pressure of 0.60 MPa, and after 5 minutes, 30 g of norbornene was pumped, and ethylene and norbornene copolymerization was carried out at 1201:. After drying, 888 g of a polymer was obtained.
( 6 )采用 CAT Π -1催化剂的聚合过程 6  (6) Polymerization process using CAT Π -1 catalyst 6
乙烯和曱基丙烯酸曱酯共聚合： 在 10L 的高压聚合反应釜中同时 加入 2. 05g负载型催化剂、 1400ml助催化剂三乙基铝（TEA )溶液（浓 度为 15wt % ) 以及 5L对二甲苯溶剂， 开启搅拌速度为 500 rpm, 然 后通入乙烯到聚合压力 0. 40MPa、 5分钟后泵入 100g甲基丙烯酸曱酯， 在 110°C下进行乙烯和甲基丙烯酸曱酯共聚合。 经干燥得到 2460g 聚 合物。  Copolymerization of ethylene and decyl methacrylate: In a 10 L high pressure polymerization reactor, 2. 05 g of supported catalyst, 1400 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of p-xylene solvent were simultaneously added. The stirring speed was 500 rpm, and then ethylene was fed to a polymerization pressure of 0.40 MPa. After 5 minutes, 100 g of decyl methacrylate was pumped, and ethylene and methacrylate methacrylate copolymerization was carried out at 110 °C. After drying, 2460 g of a polymer was obtained.
( 7 )采用 CAT Π -1催化剂的聚合过程 7  (7) Polymerization process using CAT Π -1 catalyst 7
乙浠和丙烯共聚合： 在 10L的高压聚合反应釜中同时加入 72nig负 载型催化剂、 2ml 三甲基铵四苯基硼溶液（浓度为 15g/L ) 以及 5L 己 烷溶剂， 开启搅拌速度为 150 rpm, 通入乙烯到聚合压力 0· 85MPa、 5 分钟后泵入 60g丙烯， 在 80°C下进行乙烯和丙烯共聚合。 经干燥得到 388· 8g聚合物。  Co-polymerization of acetamidine and propylene: In a 10L high-pressure polymerization reactor, simultaneously add 72nig supported catalyst, 2ml of trimethylammonium tetraphenylboron solution (concentration of 15g/L) and 5L of hexane solvent, and the stirring speed is 150. At rpm, ethylene was fed to a polymerization pressure of 0·85 MPa, and after 5 minutes, 60 g of propylene was pumped, and ethylene and propylene were copolymerized at 80 °C. After drying, 388·8 g of a polymer was obtained.
( 8 )采用 CAT Π -1催化剂的聚合过程 8  (8) Polymerization process using CAT Π -1 catalyst 8
乙烯与辛烯共聚合： 在 10L 的高压聚合反应釜中同时加入 276mg 负载型催化剂、 1ml 三甲基膦四苯基硼溶液（浓度为 10g/L ) 以及 5L 己烷溶剂， 开启搅拌速度为 150 rpm, 5 分钟后泵入 45g 辛烯， 然后 通入乙烯到聚合压力 0. 85MPa， 在 80τΐ下进行乙烯与辛烯共聚合。 经 干燥得到 883. 2g聚合物。 Copolymerization of ethylene and octene: In a 10 L high pressure polymerization reactor, 276 mg of supported catalyst, 1 ml of trimethylphosphine tetraphenylboron solution (concentration of 10 g / L) and 5 L of hexane solvent were added simultaneously, and the stirring speed was started. 150 rpm, pumping 45g of octene after 5 minutes, then Ethylene was fed to a polymerization pressure of 0.85 MPa, and ethylene and octene were copolymerized at 80 Torr. After drying, 883. 2 g of a polymer was obtained.
( 9 )采用 CAT Π -1催化剂的聚合过程 9 、  (9) Polymerization process using CAT Π -1 catalyst 9 .
乙烯均聚： 在 1 0L的高压聚合反应釜中同时加入 164mg 负载型催 化剂、 5m三异丁基硼溶液（浓度为 20g/L ) 以及 5L 己烷溶剂， 开启 搅拌速度为 150 rpm, 通入乙烯到聚合压力 0. 85MPa， 在 801下进行 乙埽均聚合。 经干燥得到 1262· 8g聚合物。  Ethylene homopolymerization: In a 10 L high pressure polymerization reactor, 164 mg of supported catalyst, 5 m of triisobutylboron solution (concentration of 20 g/L) and 5 L of hexane solvent were added simultaneously, and the stirring speed was 150 rpm, and ethylene was introduced. The polymerization was carried out at a polymerization pressure of 0.885 MPa at 801. After drying, 1262·8 g of a polymer was obtained.
( 1 0 )采用 CAT Π -1催化剂的聚合过程 10  (10) Polymerization process using CAT Π-1 catalyst 10
乙烯与苯乙烯共聚合： 在 10L的高压聚合反应釜中同时加入 40mg 负载型催化剂、 28ml助催化剂三乙基铝（TEA )溶液（浓度为 15wt % ) 以及 5L己烷溶剂， 开启搅拌速度为 400 rpm, 然后通入乙烯到聚合压 力 0. 85MPa、 5分钟后泵入 40g苯乙烯， 在 80Ό下进行乙烯和苯乙烯 共聚合。 经干燥得到 64g聚合物。  Copolymerization of ethylene and styrene: 40 mg of supported catalyst, 28 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of hexane solvent were added simultaneously in a 10 L high pressure polymerization reactor, and the stirring speed was 400. After rpm, ethylene was introduced to a polymerization pressure of 0.85 MPa, and after 5 minutes, 40 g of styrene was pumped, and ethylene and styrene were copolymerized at 80 Torr. After drying, 64 g of a polymer was obtained.
( 11 )采用 CAT Π - 1催化剂的聚合过程 11  (11) Polymerization process using CAT Π - 1 catalyst 11
氢调下乙烯与苯乙烯共聚： 在 10L 的高压聚合反应釜中同时加入 40mg负载型催化剂、 28ml助催化剂三乙基铝（ TEA )溶液（浓度为 15wt % )以及 5L己烷溶剂， 开启搅拌速度为 400 rpm, 加入氢气到 0. 3MPa , 然后通入乙烯到聚合压力 0. 85MPa、 5分钟后泵入 40g苯乙烯， 在 80 °C下进行乙烯和苯乙烯共聚合。 经干燥得到 44g聚合物。  Copolymerization of ethylene and styrene under hydrogen adjustment: 40 mg of supported catalyst, 28 ml of cocatalyst triethylaluminum (TEA) solution (concentration of 15 wt%) and 5 L of hexane solvent were added simultaneously in a 10 L high pressure polymerization reactor to open the stirring speed. To 400 rpm, hydrogen was added to 0.3 MPa, and ethylene was introduced to a polymerization pressure of 0.85 MPa. After 5 minutes, 40 g of styrene was pumped in, and ethylene and styrene were copolymerized at 80 °C. After drying, 44 g of a polymer was obtained.
( 12 )采用 CAT Π -1催化剂的聚合过程 12  (12) Polymerization process using CAT Π -1 catalyst 12
乙烯均聚： 在 10L的高压气相聚合反应釜中同时加入 200nig 负载 型催化剂、 20ml三乙基铝（浓度为 15wt% )、 0. 2L己烷溶剂、 以及 100g 无水氯化钠， 开启搅拌速度为 50 rpm, 通入乙烯到聚合压力 2. 0MPa， 在 80Ό下进行乙烯气相均聚合 经干燥除去氯化钠后得到 680g 聚合 物。  Ethylene homopolymerization: 200 nig supported catalyst, 20 ml of triethylaluminum (concentration: 15 wt%), 0.2 L of hexane solvent, and 100 g of anhydrous sodium chloride were added simultaneously in a 10 L high pressure gas phase polymerization reactor to open the stirring speed. At 50 rpm, ethylene was fed to a polymerization pressure of 2.0 MPa, and ethylene gas phase homopolymerization was carried out at 80 Torr. After drying to remove sodium chloride, 680 g of a polymer was obtained.
( 13 ) 采用 CAT Π -1催化剂的聚合过程 13  ( 13 ) Polymerization process using CAT Π -1 catalyst 13
乙烯与己烯共聚： 在 10L的高压气相聚合反应釜中同时加入 200mg 负载型催化剂、 20ml三乙基铝 （浓度为 15wt% ) 、 0. 2L己烷溶剂、 以 及 1 00g 无水氯化钠， 开启搅拌速度为 50 rpm, 通入乙烯到聚合压力 2. OMPa , 5分钟后加入 50g 己烯， 在 80Ό下进行乙烯与己烯气相共聚 合。 经干燥除去氯化钠后得到 540g聚合物。 ( 14 ) 采用 CAT Π -l催化剂的聚合过程 14 Copolymerization of ethylene and hexene: 200 mg of supported catalyst, 20 ml of triethylaluminum (concentration: 15 wt%), 0.2 L of hexane solvent, and 100 g of anhydrous sodium chloride were simultaneously added to a 10 L high pressure gas phase polymerization reactor. The stirring speed was 50 rpm, ethylene was fed to a polymerization pressure of 2. OMPa, and after 5 minutes, 50 g of hexene was added, and ethylene and hexene gas phase copolymerization was carried out at 80 Torr. After drying to remove sodium chloride, 540 g of a polymer was obtained. (14) Polymerization process using CAT Π -l catalyst 14
乙烯与辛烯共聚： 在 10L的高压气相聚合反应釜中同时加入 200mg 负载型催化剂、 20ml三乙基铝 （浓度为 15wt% ) 、 0. 2L己烷溶剂、 以 及 100g 无水氯化钠， 开启搅拌速度为 50 rpm, 通入乙烯到聚合压力 2. OMPa, 5分钟后加入 50g辛烯， 在 801C下进行乙烯与辛烯气相共聚 合。 经干燥除去氯化钠后得到 500g聚合物。 实施例 I I-2  Copolymerization of ethylene and octene: 200 mg of supported catalyst, 20 ml of triethylaluminum (concentration: 15 wt%), 0.2 L of hexane solvent, and 100 g of anhydrous sodium chloride were simultaneously added in a 10 L high pressure gas phase polymerization reactor. The stirring speed was 50 rpm, ethylene was fed to a polymerization pressure of 2. OMPa, and after 5 minutes, 50 g of octene was added, and ethylene and octene gas phase copolymerization was carried out at 801C. After drying to remove sodium chloride, 500 g of a polymer was obtained. Example I I-2
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
复合载体制备过程中， 称取 2克无水氯化镁， 加入 40ml THF, 滴 加 5ml无水乙醇， 在 50Ό下搅拌 2小时充分溶解后， 直接加入 2g热 活化的 ES70二氧化硅， 50Ό下继续搅拌 4h， 将混合液用 20ml χ 4 甲 苯洗涤、 过滤， 最后真空干燥， 得到复合载体。  During the preparation of the composite carrier, 2 g of anhydrous magnesium chloride was weighed, 40 ml of THF was added, 5 ml of absolute ethanol was added dropwise, and the mixture was stirred at 50 Torr for 2 hours to fully dissolve. Then, 2 g of heat-activated ES70 silica was directly added, and stirring was continued under 50 Torr. 4h, the mixture was washed with 20 ml of χ 4 toluene, filtered, and finally vacuum dried to give a composite carrier.
催化剂记为 CAT Π -2。  The catalyst was recorded as CAT Π -2.
乙烯均聚合过程同采用 CAT Π -1催化剂的聚合过程 1。 实施例 I I-3  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example I I-3
与实施例 I I-1基本相同， 但有如下改变：  It is basically the same as the embodiment I I-1, but with the following changes:
二氧化硅改为表面具有羧基基团的聚苯乙烯载体， 在 100"C， 氮 气下干燥 24小时；  Silica is changed to a polystyrene carrier having a carboxyl group on the surface, and dried at 100" C for 24 hours under nitrogen;
化学活化剂采用氟化钛；  The chemical activator uses titanium fluoride;
催化剂记为 CAT Π -3。  The catalyst was recorded as CAT Π -3.
乙烯均聚合过程同采用 CAT Π -1催化剂的聚合过程 1。 实施例 I I-4  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example I I-4
与实施例 I I-1基本相同， 但有如下改变：  It is basically the same as the embodiment I I-1, but with the following changes:
二氧化硅改为氧化锆载体， 在 500Ό， 氮气下焙烧 8小时； 化学活化剂采用溴化钛；  Silica is changed to zirconia support, calcined at 500 Torr for 8 hours under nitrogen; chemical activator is titanium bromide;
催化剂记为 CAT Π -4。  The catalyst was recorded as CAT Π -4.
乙婦均聚合过程同采用 CAT Π - 1催化剂的聚合过程 1。 实施例 11-5 The polymerization process of the MS is the same as the polymerization process using the CAT Π-1 catalyst. Example 11-5
与实施例 II - 1基本相同， 但有如下改变： It is basically the same as the embodiment II - 1, but with the following changes:
二氧化硅改为氧化钛载体， 在 40(TC, 氮气下焙烧 2小时； 化学活化剂采用金属 |¾化物破化钛； The silica is changed to a titanium oxide carrier, and calcined at 40 (TC, nitrogen for 2 hours; the chemical activator is made of metal | 3⁄4 to break the titanium;
催化剂记为 CAT Π-5。 The catalyst was recorded as CAT Π-5.
乙烯均聚合过程同采用 CAT Π- 1催化剂的聚合过程 1。 实施例 II-6 The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example II-6
与实施例 II- 1基本相同， 但有如下改变： It is basically the same as the embodiment II-1, but with the following changes:
二氧化硅改为多孔粘土， 在 100°C， 氮气下干燥 12小时； 化学活化剂采用金属卤化物氯化锆； The silica was changed to a porous clay and dried at 100 ° C for 12 hours under nitrogen; the chemical activator was a metal halide zirconium chloride;
催化剂记为 CAT Π-6。 The catalyst was recorded as CAT Π-6.
乙烯均聚合过程同采用 CAT Π-1催化剂的聚合过程 1。 实施例 Π-7 The ethylene homopolymerization process is the same as the polymerization process using a CAT Π-1 catalyst. Example Π-7
与实施例 II- 1基本相同， 但有如下改变： It is basically the same as the embodiment II-1, but with the following changes:
二氧化硅改为高岭土载体， 在 150 ， 氮气下干燥 24小时； 化学活化剂采用金属 化物氟化锆； The silica is changed to a kaolin carrier and dried under nitrogen at 150 ° for 24 hours; the chemical activator is a metal halide zirconium fluoride;
催化剂记为 CAT Π-7。 The catalyst was recorded as CAT Π-7.
乙烯均聚合过程同釆用 CAT Π-1催化剂的聚合过程 1。 实施例 II - 8 The polymerization process of ethylene in the homopolymerization process is the same as that of the CAT Π-1 catalyst. Example II - 8
与实施例 II- 1基本相同， 但有如下改变： It is basically the same as the embodiment II-1, but with the following changes:
二氧化硅改为硅藻土载体， 在 250°C， 氮气下干燥 16小时； 化学活化剂采用金属 |¾化物溴化锆； The silica is changed to a diatomaceous earth carrier and dried at 250 ° C for 16 hours under nitrogen; the chemical activator is a metal | 3⁄4 compound zirconium bromide;
催化剂记为 CAT Π-8。 The catalyst was recorded as CAT Π-8.
乙烯均聚合过程同采用 CAT Π- 1催化剂的聚合过程 1。 实施例 Π-9 The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example Π-9
与实施例 II-1基本相同， 但有如下改变： It is basically the same as Embodiment II-1, but with the following changes:
二氧化硅改为聚氯乙烯载体， 在 lOOC 氮气下干燥 12小时; 化学活化剂采用金属 1¾化物碘化锆； The silica was changed to a polyvinyl chloride carrier and dried under nitrogen at 10 C for 12 hours; The chemical activator uses a metal 13⁄4 compound zirconium iodide;
催化剂记为 CAT Π -9。  The catalyst was recorded as CAT Π -9.
乙烯均聚合过程同采用 CAT Π -1催化剂的聚合过程 1。 实施例 11-10  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example 11-10
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅改为聚甲基丙烯酸酯载体， 在 150Ό , 氮气下干燥 8 小 时；  The silica was changed to a polymethacrylate carrier and dried at 150 Torr for 8 hours under nitrogen;
化学活化剂采用金属卤化物氟化铝；  The chemical activator uses a metal halide aluminum fluoride;
催化剂记为 CAT Π - 10。  The catalyst was recorded as CAT Π - 10.
乙烯均聚合过程同采用 CAT Π -l催化剂的聚合过程 1。 实施例 11-11  The ethylene homopolymerization process is the same as the polymerization process using CAT Π -l catalyst. Example 11-11
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅改为氧化硅和氧化钛混合载体， 在 4 00 TC , 氮气下焙烧 8 小时；  Silica was changed to a mixed carrier of silica and titania, and calcined at 400 TC for 8 hours under nitrogen;
化学活化剂采用金属卤化物溴化铝；  The chemical activator uses a metal halide aluminum bromide;
催化剂记为 CAT Π - 11。  The catalyst was recorded as CAT Π - 11.
乙烯均聚合过程同采用 CAT Π -1催化剂的聚合过程 1。 实施例 11-12  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example 11-12
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅改为二氧化硅和溴化镁复合载体， 其中二氧化硅在 400 °C， 氮气下焙烧 12小时；  The silica is changed to a composite carrier of silica and magnesium bromide, wherein the silica is calcined at 400 ° C for 12 hours under nitrogen;
化学活化剂采用金属 |¾化物碘化铝；  The chemical activator is made of metal |3⁄4 compound aluminum iodide;
催化剂记为 CAT Π -12。  The catalyst was recorded as CAT Π -12.
乙烯均聚合过程同采用 CAT Π -l催化剂的聚合过程 1。 实施例 11-13  The ethylene homopolymerization process is the same as the polymerization process using CAT Π -l catalyst. Example 11-13
与实施例 II- 1基本相同， 但有如下改变：  It is basically the same as the embodiment II-1, but with the following changes:
二氧化硅改为膨润土载体， 在 200Ό， 氮气下干燥 8小时； 催化剂记为 CAT Π-13α The silica was changed to a bentonite carrier and dried at 200 Torr for 8 hours under nitrogen; Catalyst is recorded as CAT Π-13 α
乙烯均聚合过程同采用 CAT Π- 1催化剂的聚合过程 1。 实施例 11-14  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example 11-14
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅改为氧化镁与氧化锆混合载体， 混合载体在 450C， 氮 气下焙烧 6小时；  The silica is changed to a mixed carrier of magnesium oxide and zirconium oxide, and the mixed carrier is calcined at 450 C under nitrogen for 6 hours;
催化剂记为 CAT Π-14。  The catalyst was recorded as CAT Π-14.
乙烯均聚合过程同采用 CAT Π-l催化剂的聚合过程 1。 实施例 11-15  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-l catalyst. Example 11-15
与实施例 II- 1基本相同， 但有如下改变：  It is basically the same as the embodiment II-1, but with the following changes:
二氧化硅改为 MCM-41型分子筛载体， 在 氮气下焙烧 4小 时；  Silica was changed to MCM-41 molecular sieve carrier and calcined under nitrogen for 4 hours;
催化剂记为 CAT Π-15。  The catalyst was recorded as CAT Π-15.
乙烯均聚合过程同采用 CAT Π- 1催化剂的聚合过程 1。 实施例 Π- 16  The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. EXAMPLES Π - 16
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅改为而氧化硅和蒙脱土混合载体， 混合载体在 200°C， 氮气下焙烧 12小时；  The silica was changed to a mixed carrier of silica and montmorillonite, and the mixed carrier was calcined at 200 ° C for 12 hours under nitrogen;
催化剂记为 CAT Π-16。  The catalyst was recorded as CAT Π-16.
乙烯均聚合过程同采用 CAT Π-1催化剂的聚合过程 1。 实施例 11-17  The ethylene homopolymerization process is the same as the polymerization process using a CAT Π-1 catalyst. Example 11-17
与实施例 Π-1基本相同， 但有如下改变：  It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅的热活化条件为在氮气， 400'C下焙烧 8小时。  The thermal activation conditions of the silica were calcined under nitrogen at 400 ° C for 8 hours.
催化剂记为 CAT Π-17。  The catalyst was recorded as CAT Π-17.
乙烯均聚合过程同采用 CAT Π-l催化剂的聚合过程 1。 实施例 11-18 The ethylene homopolymerization process is the same as the polymerization process using a CAT®-l catalyst. Example 11-18
与实施例 II- 1基本相同， 但有如下改变： It is basically the same as the embodiment II-1, but with the following changes:
二氧化硅的热活化条件为在氩气， 200Ό下焙烧 12小时。 催化剂记为 CAT Π-18。 The thermal activation conditions of the silica were calcined under argon at 200 Torr for 12 hours. The catalyst was recorded as CAT Π-18.
乙烯均聚合过程同采用 CAT Π- 1催化剂的聚合过程 1。 实施例 11-19 The ethylene homopolymerization process is the same as the polymerization process using CAT Π-1 catalyst. Example 11-19
与实施例 Π- 1基本相同， 但有如下改变： It is basically the same as the embodiment Π-1, but with the following changes:
二氧化硅的热活化条件为在氮气， lOO'C下干燥 24小时, 催化剂记为 CAT Π-19。 The thermal activation conditions of the silica were dried under nitrogen, 100 ° C for 24 hours, and the catalyst was designated as CAT Π-19.
乙烯均聚合过程同采用 CAT Π-1催化剂的聚合过程 1。 The ethylene homopolymerization process is the same as the polymerization process using a CAT Π-1 catalyst.
实施例 Π- 1~ Π- 19聚合效果一览表 EXAMPLES Π- 1~ Π- 19 polymerization effect list
(采用 10升聚合反应釜聚合， 聚合反应时间均为 2小时) 溶細  (Polymerized in a 10 liter polymerization reactor, the polymerization time is 2 hours)
负载型非茂金属 催化剂活性 Supported non-metallocene catalyst activity
聚合过程 助催化剖 催 量 助催 量 聚合温度 ( *C ) 溶剂 聚合型式 聚合 力 （MPa) 堆密度 (g/cm3) 催化剂 (KgPE/gCat) Polymerization Process Promotes Catalytic Diversion Amount of Polymerization Temperature (*C) Solvent Polymerization Type Polymerization Force (MPa) Bulk Density (g/cm 3 ) Catalyst (KgPE/gCat)
(g) (g)  (g) (g)
CAT Π-1 1 ΤΕλ 0.01 0.15 50 己烷 乙烯均聚 2.0 15.4 0.35  CAT Π-1 1 ΤΕλ 0.01 0.15 50 hexane ethylene homopolymer 2.0 15.4 0.35
氢调乙烯均聚（氢  Hydrogen ethylene homopolymerization (hydrogen
CAT Π— 1 2 漏 0.10 1.0 100 甲苯 0.8 5.7 0.34  CAT Π — 1 2 Leak 0.10 1.0 100 Toluene 0.8 5.7 0.34
气 0_ 3MPa )  Gas 0_ 3MPa )
乙丁共聚  Ethylene copolymerization
CAT Π-1 3 TEA 0.008 0-56 80 癸烷 0.2 1.3 0.33  CAT Π-1 3 TEA 0.008 0-56 80 decane 0.2 1.3 0.33
(丁烯 40g)  (butene 40g)
乙己共  B.
CAT H-l 4 IBAL 0.004 148.5 60 辛烷 0.85 4.6 0.27  CAT H-l 4 IBAL 0.004 148.5 60 Octane 0.85 4.6 0.27
(己烯 20g)  (hexene 20g)
乙埽和降水片烯共  Acetyl and precipitation tablets
CAT E-l 5 EAO 0.024 116.6 120 乙苯 聚合 0.60 7.4 0.28  CAT E-l 5 EAO 0.024 116.6 120 Ethylbenzene Polymerization 0.60 7.4 0.28
(降冰片烯 30g)  (norbornene 30g)
乙烯和曱基丙烯酸  Ethylene and mercaptoacrylic acid
CAT Π-1 6 TEA 0.41 56 110 对二甲苯 曱硗共聚（曱基丙 0.40 1.2 0.25  CAT Π-1 6 TEA 0.41 56 110 p-xylene 曱硗 copolymerization (mercaptopropyl 0.40 1.2 0.25
烯酸甲醋 100g )  Acetate vinegar 100g )
三曱基镇四 乙丙共聚  Sanjiaji Town, Tetraethylene Propylene Copolymer
CAT Π— 1 7 0.0144 0.03 80 己烷 0.85 5.4 0- 29  CAT Π — 1 7 0.0144 0.03 80 Hexane 0.85 5.4 0- 29
苯基硼 (丙烯 60g)  Phenyl boron (propylene 60g)
三曱基膦四 Trimethylphosphine tetra
0 乙辛共聚  0 Ethylene copolymerization
CAT Π-1 8 0- 0552 0. 02 80 己烷 0.85 3.2 0.30  CAT Π-1 8 0- 0552 0. 02 80 hexane 0.85 3.2 0.30
苯基硼 (辛烯 45g)  Phenyl boron (octene 45g)
CAT H-l 9 三异丁基裯 0.0328 0.02 80 己烷 乙烯均聚 0.85 7.7 0.30  CAT H-l 9 Triisobutylhydrazine 0.0328 0.02 80 Hexane Ethylene homopolymerization 0.85 7.7 0.30
乙烯和苯乙烯共聚  Copolymerization of ethylene and styrene
CAT H-l 10 TEA 0.008 0.56 80 己坑 0.85 1.6 0.33  CAT H-l 10 TEA 0.008 0.56 80 hang pit 0.85 1.6 0.33
(苯乙烯 40g)  (styrene 40g)
乙烯和苯乙婦共聚  Ethylene and styrene copolymerization
CAT H— 1 11 ΤΕλ 0.008 0.56 80 己坑 (氢气 0.3 Pa， 苯 0.85 L1 0.33  CAT H— 1 11 ΤΕλ 0.008 0.56 80 pit (hydrogen 0.3 Pa, benzene 0.85 L1 0.33
乙烯 40g)  Ethylene 40g)
CAT Π-1 12 TEA 0.04 - 80 ― 气相乙烯均聚 2.0 3.4 0.32  CAT Π-1 12 TEA 0.04 - 80 ― Gas phase ethylene homopolymerization 2.0 3.4 0.32
气相乙己共乘  Gas phase
CAT Π - 1 13 TEA. 0.04 - 80 2.0 2.7 0.31  CAT Π - 1 13 TEA. 0.04 - 80 2.0 2.7 0.31
(己烯 50g)  (hexene 50g)
CAT Π-1 14 TEA. 0.04 - 相乙辛共聚  CAT Π-1 14 TEA. 0.04 - Phase Ethylene Copolymer
80 ― 气  80 ― gas
2.0 2.5 0.30 (辛烯 50g) 2.0 2.5 0.30 (octene 50 g )
实施例 Π- 1― 11-19聚合效果一览表 (续） 斜溶剂用 EXAMPLES Π-1 1-11 Polymerization Effect List (Continued)
负载型非茂金属 催化剤活性 Supported non-metallocene catalyzed ruthenium activity
聚 程 助催化剂 催僻】量 助催 量 聚合温度 ( 'C ) 溶剖 聚合.型式 聚合压力（MPa) 堆密度 fe/cm3 催化剂 (KgPE/gCat ) Concentration cocatalyst catalyzed] Amount of assisted polymerization temperature ( 'C ) Dissolution polymerization. Type polymerization pressure (MPa) Bulk density fe/cm 3 catalyst (KgPE/gCat)
(g) (g)  (g) (g)
CAT Π-2 1 TEA 0.01 0.15 85 己坑 乙烯均聚 2.0 11.2 0.31 CAT Π-2 1 TEA 0.01 0.15 85 hex pit ethylene homopolymer 2.0 11.2 0.31
CAT Π-3 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 9.7 0.28CAT Π-3 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 9.7 0.28
CAT Π-4 1 TEA 0.01 0.15 85 己坑 乙烯均聚 2.0 7.6 0.27CAT Π-4 1 TEA 0.01 0.15 85 hex pit ethylene homopolymerization 2.0 7.6 0.27
CAT Π-5 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 8.4 0.30CAT Π-5 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 8.4 0.30
CAT Π-6 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 10.4 0.27CAT Π-6 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 10.4 0.27
CAT Π-7 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 9.4 0.29CAT Π-7 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 9.4 0.29
CAT Π-8 1 TEA 0.01 0.15 85 己坑 乙烯均聚 2.0 10.1 0.30CAT Π-8 1 TEA 0.01 0.15 85 hex pit ethylene homopolymer 2.0 10.1 0.30
CAT Π-9 1 TEA- 0.01 0.15 85 己烷 乙烯均聚 2.0 7.2 0.27CAT Π-9 1 TEA- 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 7.2 0.27
CAT Π-10 1 TEA 0.01 0.15 85 己號 乙烯均聚 2.0 6.4 0.26CAT Π-10 1 TEA 0.01 0.15 85 No. Ethylene homopolymerization 2.0 6.4 0.26
CAT Π-11 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 11.8 0.32CAT Π-11 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymer 2.0 11.8 0.32
CAT Π-12 1 TBA 0.01 0.15 85 己烷 乙烯均聚 2.0 12.1 0.32CAT Π-12 1 TBA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 12.1 0.32
CAT Π-13 1 TEA 0.01 0—15 85 己垸 乙烯均聚 2.0 8.8 0.29CAT Π-13 1 TEA 0.01 0—15 85 hexanes Ethylene homopolymerization 2.0 8.8 0.29
CAT Π-14 1 TEA 0.01 0.15 85 己坑 乙婦均聚 2.0 5.7 0.28CAT Π-14 1 TEA 0.01 0.15 85 己坑 乙妇均聚 2.0 5.7 0.28
CAT Π-15 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 10.7 0.30CAT Π-15 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymer 2.0 10.7 0.30
CAT Π-16 1 TEA 0.01 0.15 85 己炕 乙烯均聚 2.0 11.4 0.30CAT Π-16 1 TEA 0.01 0.15 85 hexene Ethylene homopolymer 2.0 11.4 0.30
CAT Π-17 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 14.7 0.34CAT Π-17 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 14.7 0.34
CAT Π-18 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 14.1 0.33CAT Π-18 1 TEA 0.01 0.15 85 Hexane Ethylene homopolymerization 2.0 14.1 0.33
CAT Π-19 1 TEA 0.01 0.15 85 己烷 乙烯均聚 2.0 13.7 0.30 CAT Π-19 1 TEA 0.01 0.15 85 Hexane ethylene homopolymer 2.0 13.7 0.30
负载型非茂金属烯烃聚合催化剂左淤桨聚合中应用的^施例 Application of supported non-metallocene olefin polymerization catalyst in left slurry polymerization
在以下实施例中， 制备了本发明的负载型非茂金属烯烃聚合催化 剂， 并将其用于乙烯的淤浆聚合中。 实施例 3-1  In the following examples, the supported non-metallocene olefin polymerization catalyst of the present invention was prepared and used in slurry polymerization of ethylene. Example 3-1
制备负载型非茂金属催化剂  Preparation of supported non-metallocene catalysts
( 1 )二氧化硅的热活化处理  (1) Thermal activation treatment of silica
取 ES70型二氧化硅（Ineos公司产品）在氮气气氛下焙烧。 其焙烧 条件为： 升温速率 5。C /Min， 200'C下恒温 0. 5h， 400°C下恒温 0. 5h， 然 后在 600°C下恒温 4h， 最后在氮气氛下自然冷却。 记为 ES70- 650载体。  ES70 type silica (product of Ineos) was calcined under a nitrogen atmosphere. The firing conditions are: heating rate 5. C / Min, constant temperature at 200 ° C 0. 5h, constant temperature at 400 ° C 0. 5h, then constant temperature at 600 ° C for 4h, and finally cooled naturally under nitrogen atmosphere. Recorded as ES70-650 carrier.
( 2 )修饰载体的制备  (2) Preparation of modified carrier
取 10gES70-650载体，加入 200ml甲苯，搅拌下加入 50ml TiCl4( 5v/v% TiCl4己烷溶液） ， 20°C下搅拌反应 16小时， 过滤， 用 150ml甲苯分三 次洗涤、 干燥和真空抽干。 Take 10g of ES70-650 carrier, add 200ml of toluene, add 50ml of TiCl 4 (5v/v% TiCl 4 hexane solution) with stirring, stir the reaction at 20 ° C for 16 hours, filter, wash with 150ml of toluene three times, dry and vacuum dry.
( 3 )复合载体的制备  (3) Preparation of composite carrier
将分析纯氯化镁在 500 C、 空气气氛下煅烧 3h制得无水氯化镁。 在 无水无氧的氮气氛下 （水和氧的含量均低于 5ppm ) ， 称取 10克无水氯 化镁， 加入 200ml四氢呋喃， 滴加 25ml无水乙醇（3A分子筛浸泡 4 日）。 氯化镁完全溶解后， 再加入前述载体， 50 下搅拌 4h， 过滤， 用 240ml 甲苯分三次洗涤， 最后干燥和真空抽干， 得 19. 9g复合载体。  Anhydrous magnesium chloride was prepared by calcining pure magnesium chloride at 500 C in an air atmosphere for 3 hours. Under an anhydrous and oxygen-free nitrogen atmosphere (water and oxygen contents are less than 5 ppm), 10 g of anhydrous magnesium chloride is weighed, 200 ml of tetrahydrofuran is added, and 25 ml of absolute ethanol (3A molecular sieve soaked for 4 days) is added dropwise. After the magnesium chloride was completely dissolved, the above carrier was further added, stirred at 50 for 4 hours, filtered, washed three times with 240 ml of toluene, finally dried and vacuum dried to give 19.9 g of a composite carrier.
( 4 )修饰复合载体的制备  (4) Preparation of modified composite carrier
加入 180ml甲苯到 19. 9 g复合载体中， 滴加 20ml曱基铝氧烷（ 10wt %MA0曱苯溶液）和 5mlTiCl4， 20°C下搅拌反应 2小时。 过滤， 用 240ml 甲苯分三次洗涤， 最后干燥和真空抽干。 180 ml of toluene was added to a 19.9 g composite carrier, 20 ml of mercaptoaluminoxane (10 wt% MA0 oxime solution) and 5 ml of TiCl 4 were added dropwise, and the reaction was stirred at 20 ° C for 2 hours. It was filtered, washed three times with 240 ml of toluene, finally dried and vacuum dried.
( 5 ) 负载型非茂金属催化剂的制备  (5) Preparation of supported non-metallocene catalyst
称取修饰复合载体 5g, 与 1. 25g
Figure imgf000054_0001
的非茂 金属催化剂和 7ml四氢呋喃组成的溶液进行等体积浸渍， 并充分搅拌均 匀， 最后抽干。 得到干的、 可流动、 桔红色的负载型催化剂。 5克。 With the modified composite carrier 5g, with 1. 25g
Figure imgf000054_0001
Non-mao A solution of a metal catalyst and 7 ml of tetrahydrofuran was impregnated in an equal volume, stirred well, and finally drained. A dry, flowable, orange-red supported catalyst is obtained.
催化剂记为 CAT-1。  The catalyst was recorded as CAT-1.
采用上述负载型非茂金属催化剂的淤浆聚合过程：  Slurry polymerization process using the above supported non-metallocene catalyst:
负载型非茂金属催化剂与助催化剂组成催化体系， 直接用于乙烯淤浆 法聚合。  The supported non-metallocene catalyst and the cocatalyst constitute a catalytic system and are directly used for the polymerization of ethylene slurry.
为了调节聚合物的熔^指数， 在聚合过程使用氢气作为链转移剂。 使用的氢气量可在总气体量的 0. 01 0. 99 (体积比） 。  In order to adjust the melting index of the polymer, hydrogen is used as a chain transfer agent in the polymerization process. The amount of hydrogen used may be 0.011. 99 (volume ratio) of the total gas amount.
本实施例所涉及到的溶剂是己烷。  The solvent involved in this example is hexane.
洗涤、 过滤、 干燥和抽干， 本实施例采用抽滤方法： 将需要洗涤过 滤的体系到入砂芯漏斗中， 通过抽滤作用抽去溶剂， 然后再加入溶剂， 再抽滤， 从而达到洗涤过滤的目的。 洗涤过滤过程优选重复 2 ~ 4次。  Washing, filtering, drying and drying, this embodiment adopts the suction filtration method: the system to be washed and filtered is put into the sand core funnel, the solvent is removed by suction filtration, and then the solvent is added, and then filtered, thereby washing. The purpose of filtration. The washing and filtering process is preferably repeated 2 to 4 times.
将固体在温度约为 0 ~ 120Ό下进行减压干燥， 直到获得流动性的催 化剂载体粉末为止。 这个干燥过程时间的长短依赖于所用温度， 以及真 空系统的能力和体系的密闭情况有关。  The solid is dried under reduced pressure at a temperature of about 0 to 120 Torr until a fluid catalyst carrier powder is obtained. The length of this drying process depends on the temperature used and the capacity of the vacuum system and the containment of the system.
以上所述的载体的化学处理过程和非茂金属烯烃聚合催化剂的负载 过程均需要在严格的无水无氧条件下进行， 这里所说的无水无氧条件是 指体系中水和氧的含量持续小于 10ppm， 无水无氧条件是获得高活性负 载型催化剂的关键因素之一。  The chemical treatment process of the above-mentioned carrier and the loading process of the non-metallocene olefin polymerization catalyst need to be carried out under strict anhydrous and anaerobic conditions, and the anhydrous anaerobic conditions referred to herein refer to the water and oxygen contents in the system. For less than 10 ppm, anhydrous anaerobic conditions are one of the key factors in obtaining a highly active supported catalyst.
充分地洗涤过滤、 干燥抽干过程也是荻得高活性和良好粒子形态聚 合物的关键。 洗涤过滤过程除去游离态的物质， 干燥抽干可以获得反应 物质的良好结合力。 实施例 3 - 2  Adequate washing filtration, dry drying, and drying are also key to achieving high activity and good particle morphology. The washing and filtering process removes the free matter, and drying and drying can obtain a good binding force of the reaction substance. Example 3 - 2
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
催化剂的制备中二氧化硅采用 ES70X, 催化剂记为 CAT-2;  In the preparation of the catalyst, silica is ES70X, and the catalyst is recorded as CAT-2;
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 1基本 相同， 但助催化剂选用乙基铝氧烷 ( EA0 ) 。 实施例 3-3  The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as in Example 1, except that the cocatalyst was selected from ethylaluminoxane (EA0). Example 3-3
与实施例 3-1基^目同， 但有如下改变：  Same as the embodiment 3-1, but with the following changes:
催化剂的制备中二氧化硅为 ES70Y, 催化剂记为 CAT- 3。 助催化剂选用异丁基铝氧烷 ( IBA0 )； In the preparation of the catalyst, the silica was ES70Y, and the catalyst was recorded as CAT-3. The catalyst is selected from isobutyl aluminoxane ( IBA0 );
本实施例的溶剂是四氢呋喃；  The solvent of this embodiment is tetrahydrofuran;
氯化镁改为乙氧基镁。 实施例 3-4  Magnesium chloride was changed to ethoxy magnesium. Example 3-4
与实施例 3-1基^目同， 但有如下改变：  Same as the embodiment 3-1, but with the following changes:
催化剂的制备中二氧化硅为中空二氧化硅， 催化剂记为 CAT- 4;  In the preparation of the catalyst, the silica is hollow silica, and the catalyst is referred to as CAT-4;
氯化镁改为烷氧基卤化镁、 烷氧基镁的混合物。 实施例 3-5  Magnesium chloride is changed to a mixture of alkoxymagnesium halide and alkoxymagnesium. Example 3-5
与实施例 3-1 ^相同， 但有如下改变：  Same as Example 3-1 ^, but with the following changes:
催化剂的制备中载体为载体为氧化铝和氧化硅的混合物（氧化铝和 氧化硅质量比为 1: 2 )；  In the preparation of the catalyst, the carrier is a mixture of alumina and silica (the mass ratio of alumina to silica is 1: 2 );
催化剂的制备用 2mlMA0 ( 10wt %甲苯溶液）代替 20mlMAO ( 10wt % 甲苯溶液） ；  The catalyst was prepared by replacing 2 ml of MAO (10 wt% in toluene solution) with 20 ml of MAO (10 wt% in toluene solution);
而且本实施例催化剂的制备中没有实施例 3-1中的第 1步磔 "热活 化处理" 与第 4步骤 "修饰复合载体的制备" ；  Further, in the preparation of the catalyst of this example, there is no first step "heat activation treatment" in the embodiment 3-1 and "step preparation" of the modified composite carrier in the fourth step;
氯化镁改为氯化镁与乙氧基氯化镁的混合物（氯化鎂与乙氧基氯化 镁质量必为 4: 1 ) 。  Magnesium chloride is changed to a mixture of magnesium chloride and ethoxymagnesium chloride (magnesium chloride and ethoxylated magnesium chloride must be 4:1).
化学处理剂选用三乙基铝 ( TEA )；  The chemical treatment agent is selected from triethyl aluminum (TEA);
催化剂制备用溶剂为戊烷。 实施例 3-6  The solvent for catalyst preparation is pentane. Example 3-6
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
载体为由 SiH4经过其相水解得到的二氧化硅。 The support is silica obtained by hydrolysis of SiH 4 through its phase.
催化剂的制备用 20ml三乙基铝 ( 0. 43mol/l己烷溶液）代替 20mlMA0 ( 10wt %甲苯溶液） ， 催化剂记为 CAT-6。 实施例 3 - 7  The catalyst was prepared by replacing 20 ml of MA0 (10 wt% in toluene solution) with 20 ml of triethylaluminum (0.43 mol/l hexane solution), and the catalyst was designated as CAT-6. Example 3 - 7
与实施例 3-1基^目同， 但有如下改变：  Same as the embodiment 3-1, but with the following changes:
载体为聚苯乙烯， 表面具有乙氧基官能团。  The support is polystyrene and the surface has an ethoxy functional group.
修饰复合载体不用甲基铝氧烷； 非茂金属催化剂负载时， 5g修饰复 合载体与 1. 5g非茂金属催化剂的 20ml四氢呋喃溶液浸渍后直接抽干。 载体选择氧化铝。 The modified composite carrier does not use methylaluminoxane; when the non-metallocene catalyst is loaded, 5g is modified. The carrier was impregnated with a solution of 1.5 g of a non-metallocene catalyst in 20 ml of tetrahydrofuran and directly drained. The carrier selects alumina.
催化剂制备用溶剂为癸綻。  The solvent for catalyst preparation is flawed.
催化剂记为 CAT- 7。 实施例 3-8  The catalyst was recorded as CAT-7. Example 3-8
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
载体为聚 烯载体。  The carrier is a polyolefin carrier.
修饰复合载体用 2mlMA0 ( 10wt %曱苯溶液）代替 20mlMAO ( 10wt % 甲苯溶液） ； 非茂金属催化剂负载时， 5g修饰复合载体与 1. 5g非茂金 属催化剂的 20ml曱苯溶液浸渍后直接抽干。 The modified composite carrier was replaced with 2 ml of MA0 (10 wt% benzene solution) in 20 ml of MAO (10 wt% toluene solution); when the non-metallocene catalyst was supported, 5 g of the modified composite carrier and 1.5 g of the non-metallocene catalyst were impregnated with 20 ml of the benzene solution. dry.
催化剂记为 CAT- 8。 实施例 3-9  The catalyst was recorded as CAT-8. Example 3-9
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
载体为 CS - 2133型二氧化硅。  The carrier is CS-2133 type silica.
催化剂的制备除复合载体的制备中以 39ml丁醇代替 25 ml 乙醇； 催化剂制备用溶剂为二氯乙烷。  The preparation of the catalyst was carried out by substituting 39 ml of butanol for 25 ml of ethanol in addition to the preparation of the composite carrier; the solvent for catalyst preparation was dichloroethane.
催化剂记为 CAT- 9。 实施例 3-10  The catalyst was recorded as CAT-9. Example 3-10
与实施例 3 - 1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
复合载体的制备中以 200ml己烷代替 200 ml四氢呋喃； 2mlMA0 ( 10wt %曱苯溶液）代替 20mlMAO ( 10wt %甲苯溶液） 。 催化剂记为 CAT- 10。 实施例 3-11  In the preparation of the composite carrier, 200 ml of hexane was used instead of 200 ml of tetrahydrofuran; 2 ml of MA0 (10 wt% of a solution of toluene) was used instead of 20 ml of MAO (10 wt% of toluene solution). The catalyst was recorded as CAT-10. Example 3-11
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
复合载体制备中， 以 200ml己烷代替 200 ml四氢呋喃； 20ml三乙基 铝 （0. 43mol/l ) 己烷溶液）代替 20mlMA0 ( 10wt %甲苯溶液） 。 In the preparation of the composite carrier, 200 ml of hexane was used instead of 200 ml of tetrahydrofuran; 20 ml of triethylaluminum (0.43 mol/l of hexane solution) was used instead of 20 ml of MA0 (10 wt% in toluene solution).
催化剂记为 CAT-11。 实施例 3-12 The catalyst was recorded as CAT-11. Example 3-12
催化剂的制备除采用结构式为  The preparation of the catalyst is in addition to the structural formula.
Figure imgf000058_0001
替代结构式为
Figure imgf000058_0001
The alternative structure is
茂金属催化剂外， 其余与实施例 3-1相同。 The remainder of the metallocene catalyst was the same as in Example 3-1.
催化剂记为 CAT-12。 实施例 3-13  The catalyst was recorded as CAT-12. Example 3-13
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
催化剂的制备除修饰载体的制备中以四氯化硅代替四氯化钛； 催化剂负载用溶剂环己烷。  Preparation of Catalyst In addition to the preparation of the modified support, silicon tetrachloride was used in place of titanium tetrachloride; the catalyst was supported with solvent cyclohexane.
催化剂记为 CAT-13。 实施例 3-14  The catalyst was recorded as CAT-13. Example 3-14
与实施例 3-1基^目同， 但有如下改变：  Same as the embodiment 3-1, but with the following changes:
非茂金属催化剂负载时， 5g修饰复合载体与 1. 5g非茂金属催化剂的 100ml曱苯溶液浸溃 16小时后， 过滤， 120ml甲苯分三次洗涤， 最后干 燥抽干。  When the non-metallocene catalyst was supported, 5 g of the modified composite support was impregnated with a solution of 1.5 g of a non-metallocene catalyst in 100 ml of hydrazine for 16 hours, filtered, and 120 ml of toluene was washed three times, and finally dried and drained.
催化剂记为 CAT-14。 实施例 3-15  The catalyst was recorded as CAT-14. Example 3-15
与实施例 3-1基本相同， 但有如下改变：  It is basically the same as Embodiment 3-1, but with the following changes:
载体不进行热活化， 直接与化学活化剂作用， 得到修饰载体。  The carrier is not thermally activated and acts directly with the chemical activating agent to obtain a modified carrier.
催化剂负载用溶剂为二曱苯。  The solvent for catalyst loading is diphenylbenzene.
催化剂记为 CAT-15。 实施例 3-16 The catalyst was recorded as CAT-15. Example 3-16
与实施例 3-1 1 ^目同， 但有如下改变：  Same as the embodiment 3-1 1 ^, but with the following changes:
复合载体直接与非茂金属烯烃聚合催化剂反应， 之前不与化学处理 剂作用。  The composite support is directly reacted with a non-metallocene olefin polymerization catalyst and has not previously been treated with a chemical treatment agent.
催化剂制备用溶剂为四氢呋喃。  The solvent for catalyst preparation was tetrahydrofuran.
催化剂记为 CAT-16。 The catalyst was recorded as CAT-16.
淤浆聚合反应结果一览表 催化剂活性 负载型非茂金 催化剂用量 助催化剂用 聚合釜 聚合溫度 聚合压力 聚合时间 堆密度 助催化剂 溶剂 聚合型式 (IgPE/gCa Summary of slurry polymerization results Catalyst activity Supported non-metallocene Catalyst dosage Cocatalyst Polymerization reactor Polymerization temperature Polymerization pressure Polymerization time Bulk density Cocatalyst Solvent Polymerization type (IgPE/gCa
属催化剂 (mg) 量 (ml) (L) CC ) (MPa) (h.) ( g/ml ) t)  Catalyst (mg) Amount (ml) (L) CC ) (MPa) (h.) ( g/ml ) t)
乙辛共聚（辛  Ethylene copolymerization
CAT- 1 23.4 MAO 2.3 2 65 己坑 2.0 3 21.4 0.30  CAT-1 2 23.4 MAO 2.3 2 65 pit 2.0 3 21.4 0.30
烯 30g)  Alkene 30g)
CAT- 1 19.4 TIBA 2.0 2 85 己烷 乙烯均聚 0.8 3 17.4 0.29  CAT-1 1 19.4 TIBA 2.0 2 85 Hexane Ethylene homopolymerization 0.8 3 17.4 0.29
氣调  Atmosphere
CAT- 2 23 TEA 2.3 2 65 己烷 (0. «0MPa) 2.0 2 1.17 0.23  CAT- 2 23 TEA 2.3 2 65 hexane (0. «0MPa) 2.0 2 1.17 0.23
乙烯均聚  Ethylene homopolymerization
CAT— 3 17.4 MAO 1.75 2 60 己坑 乙烯均聚 2.0 2 12.1 0.33  CAT— 3 17.4 MAO 1.75 2 60 pits Ethylene homopolymerization 2.0 2 12.1 0.33
乙烯与丁烯  Ethylene and butene
CAT-4 20 MAO 2.0 2 50 己烷 2.0 2 8.35 0.31  CAT-4 20 MAO 2.0 2 50 Hexane 2.0 2 8.35 0.31
共聚  Copolymerization
CAT— 5 22 MAO 2.2 2 85 二氯乙 : 烯均聚 0.7 4 14.7 0.335  CAT— 5 22 MAO 2.2 2 85 Dichloroethylene : olefin homopolymerization 0.7 4 14.7 0.335
氢调  Hydrogen regulation
CAT— 5 22.9 MAO 2- 3 2 85 己烷 ( 0.15 Pa ) 0.7 4 6.2 0.335  CAT— 5 22.9 MAO 2- 3 2 85 Hexane ( 0.15 Pa ) 0.7 4 6.2 0.335
乙烯均聚 Ethylene homopolymerization
M M
CAT— 6 21 TEA 2.1 2 85 己烷 ( 0.05MPa ) 0.7 4 9.3 0.32 CAT— 6 21 TEA 2.1 2 85 Hexane ( 0.05MPa ) 0.7 4 9.3 0.32
乙烯均聚  Ethylene homopolymerization
氢调  Hydrogen regulation
CAT— 7 26.3 TEA 2.7 2 85 庚坑 ( 0. OlMPa ) 0.7 3 12.4 0.26  CAT— 7 26.3 TEA 2.7 2 85 Geng pit ( 0. OlMPa ) 0.7 3 12.4 0.26
乙烯均聚 Ethylene homopolymerization
淤浆聚合反应结杲一览表 (续） Slurry polymerization balance list (continued)
Figure imgf000061_0001
Figure imgf000061_0001
在以下实施例中， 进一步制备了本发明的负载型非茂金属烯烃聚 合催化剂， 并将其用于乙烯的淤浆聚合中。 实施例 III-1 In the following examples, the supported non-metallocene olefin polymerization catalyst of the present invention was further prepared and used in slurry polymerization of ethylene. Example III-1
催化剂制备过程与实施例 1 -1基本相同， 但有如下改变： 修饰复合载体的制备过程中： 加入 40ml 曱苯到 4g复合载体中， 仅滴加 20mlTiCl4 ( 5v/v TiCl4己烷溶液） , 20°C下搅拌反应 2小时。 将混合液用 30ml曱苯洗涤、 过滤、 真空干燥后得到修饰复合载体。 The catalyst preparation process of Example 1-1 is substantially the same, but with the following changes: the preparation of a modified composite carrier: 4g was added to 40ml of benzene Yue composite carrier was added dropwise only 20mlTiCl 4 (5v / v TiCl 4 in hexane) The reaction was stirred at 20 ° C for 2 hours. The mixed solution was washed with 30 ml of hydrazine, filtered, and dried in vacuo to give a modified composite.
催化剂记为 CAT ΠΙ-1。  The catalyst was recorded as CAT ΠΙ-1.
采用上述负载型非茂金属催化剂进行淤浆聚合过程时， 助催化剂 采用甲基铝氧烷（MA0) 。  When the above-mentioned supported non-metallocene catalyst is used for the slurry polymerization process, the cocatalyst is methylaluminoxane (MA0).
负载型非茂金属催化剂与助催化剂组成催化体系， 直接用于乙烯 淤浆法聚合。 在 10升聚合反应釜中加入 23.4g 负载型催化剂， 然后 加入 2.3ml 甲基铝氧烷（MAO) (浓度为 10wt%)和 5升己烷，在 0.8MPa 乙烯总压下聚合 2小时， 搅拌速度为 250转 /分， 聚合温度为 80Ό。  The supported non-metallocene catalyst and cocatalyst constitute a catalytic system and are directly used for the polymerization of ethylene slurry. 23.4 g of supported catalyst was added to a 10 liter polymerization reactor, then 2.3 ml of methylaluminoxane (MAO) (concentration: 10 wt%) and 5 liters of hexane were added, and polymerization was carried out for 2 hours under a total pressure of 0.8 MPa of ethylene. The speed was 250 rpm and the polymerization temperature was 80 Ό.
为了调节聚合物的熔融指数， 在聚合过程使用氢气作为链转移剂。 使用的氢气量可占总气体量的 0.01- 0.99 (体积比） 。  In order to adjust the melt index of the polymer, hydrogen is used as a chain transfer agent in the polymerization process. The amount of hydrogen used can range from 0.01 to 0.99 (by volume) of the total gas.
本实施例所涉及到的溶剂是己烷。 实施例 ΙΙΙ-2  The solvent involved in this example is hexane. Example ΙΙΙ-2
与实施例 III-1基本相同， 但有如下改变：  It is basically the same as Embodiment III-1, but with the following changes:
催化剂的制备中二氧化硅采用 ES70X;  In the preparation of the catalyst, silica is ES70X;
化学活化剂采用 A1C13; The chemical activator uses A1C1 3 ;
催化剂记为 CAT m-2。  The catalyst was recorded as CAT m-2.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1基本相同， 但聚合压力为 2. OMPa, 聚合温度 501C， 助催化剂选用三 乙基铝 （TEA) ， 氢气量占总气体量的 0.4 (体积比） 。 实施例 III- 3  The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment III-1, but the polymerization pressure is 2. OMPa, the polymerization temperature is 501 C, and the promoter is selected from triethyl aluminum (TEA). The amount of gas is 0.4 (volume ratio). Example III-3
与实施例 III-1基本相同， 但有如下改变：  It is basically the same as Embodiment III-1, but with the following changes:
催化剂的制备中二氧化硅为 ES70Y;  The silica in the preparation of the catalyst is ES70Y;
化学活化剂采用 VC15; 本实施例的溶剂是四氢呋喃； The chemical activator uses VC1 5 ; The solvent of this embodiment is tetrahydrofuran;
氯化镁改为乙氧基镁。  Magnesium chloride was changed to ethoxy magnesium.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物:  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000063_0001
Figure imgf000063_0001
催化剂记为 CAT ΙΠ-3。  The catalyst was recorded as CAT ΙΠ-3.
釆用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1 基本相同， 但助催化剂选用三异丁基铝氧烷（IBA0) ， 聚合压力为 2. OMPa, 聚合温度 40 , 氢气量占总气体量的 0.4 (体积比） 。 实施例 ΙΠ-4  The polymerization temperature is 4. OMPa, the polymerization temperature is 40, and the polymerization temperature is 2. OMPa, the polymerization temperature is 40, and the polymerization temperature is 4. OMPa, the polymerization temperature is 40. The amount of hydrogen accounts for 0.4 (volume ratio) of the total gas. Example ΙΠ-4
与实施例 III- 1基本相同， 但有如下改变：  It is basically the same as the embodiment III-1, but with the following changes:
催化剂的制备中二氧化硅为中空二氧化硅；  In the preparation of the catalyst, the silica is hollow silica;
化学活化剂采用三乙基铝；  The chemical activator is triethylaluminum;
氯化镁改为烷氧基! ¾化镁、 烷氧基镁的混合物。  Magnesium chloride is changed to alkoxy! 3⁄4 mixture of magnesium and alkoxymagnesium.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物:  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000063_0002
Figure imgf000063_0002
催化剂记为 CAT ΠΙ-4。  The catalyst was recorded as CAT ΠΙ-4.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1 基本相同， 但助催化剂选用三曱基铝 （ΤΜΑ) ， 聚合压力为 1.5MPa， 聚合温度 75°C， 进行乙烯和丁烯共聚， 丁烯加入 25g。 实施例 II 1-5  The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment III-1, but the promoter is selected from tridecyl aluminum (ruthenium), the polymerization pressure is 1.5 MPa, the polymerization temperature is 75 ° C, and ethylene and Butene copolymerization, butene was added to 25 g. Example II 1-5
与实施例 III- 1基本相同， 但有如下改变：  It is basically the same as the embodiment III-1, but with the following changes:
催化剂的制备中载体为载体为氧化铝和氧化硅的混合物 （氧化铝 和氧化硅质量比为 1: 2) ， 载体在氮气氛下 800Ό焙烧 4小时；  In the preparation of the catalyst, the carrier is a mixture of alumina and silica (the mass ratio of alumina to silica is 1: 2), and the carrier is calcined at 800 Torr for 4 hours under a nitrogen atmosphere;
修饰复合载体的制备用 2mlMA0 ( 10wt%曱苯溶液）代替 20mlTiCl4 ( 5v/v% TiCl4己烷溶液） ； Preparation of modified composite carrier 2ml MA0 (10wt% benzene solution) instead of 20ml TiCl 4 (5v/v% TiCl 4 hexane solution);
氯化镁改为氯化镁与乙氧基氯化镁的混合物 （氯化镁与乙氧基氯 化镁质量必为 4: 1) 。  Magnesium chloride is changed to a mixture of magnesium chloride and ethoxymagnesium chloride (magnesium chloride and ethoxylated magnesium chloride must be 4:1).
化学处理剂选用三乙基铝 （TEA) ；  The chemical treatment agent is selected from triethyl aluminum (TEA);
催化剂制备用溶剂为戊烷。  The solvent for catalyst preparation is pentane.
化剂改为具有以下结构式的化合物：  The chemical is changed to a compound having the following structural formula:
Figure imgf000064_0001
Figure imgf000064_0001
催化剂记为 CAT ΙΠ-5。  The catalyst was recorded as CAT ΙΠ-5.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1基本相同，但助催化剂选用三乙基铝氧烷（ EA0),聚合压力为 2.5MPa, 聚合温度为 40Ό， 聚合溶剂采用二氯乙烷。 实施例 III -6  The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1, but the promoter was selected from triethylaluminoxane (EA0), the polymerization pressure was 2.5 MPa, the polymerization temperature was 40 Torr, and the polymerization solvent was used. Dichloroethane is used. Example III -6
与实施例 III-1基本相同， 但有如下改变：  It is basically the same as Embodiment III-1, but with the following changes:
载体为由 SiH4经过其相水解得到的二氧化硅。 The support is silica obtained by hydrolysis of SiH 4 through its phase.
化学活化剂采用三异丁基铝；  The chemical activator is triisobutylaluminum;
修饰复合载体的制备用 20ml三乙基铝 （0.43mol八 己烷溶液）代 替 20mlMAO ( 10wt %甲苯溶液） 。  Preparation of the modified composite carrier 20 ml of triethylaluminum (0.43 mol of octahexane solution) was used instead of 20 ml of MAO (10 wt% in toluene solution).
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000064_0002
Figure imgf000064_0002
催化剂记为 CAT ΠΙ - 6。  The catalyst was recorded as CAT ΠΙ - 6.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 111- 1基本相同， 但助催化剂选用 MA0-TEA, 聚合压力为 G.7MPa， 聚合温 度 85°C, 氢气量占总气体量的 0.071 (体积比） 。 实施例 III-7  The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment 111-1, but the promoter is selected from MA0-TEA, the polymerization pressure is G.7 MPa, the polymerization temperature is 85 ° C, and the amount of hydrogen accounts for the total gas amount. 0.071 (volume ratio). Example III-7
与实施例 III-1基本相同， 但有如下改变: 载体为聚苯乙烯， 表面具有羧基官能团。 It is basically the same as Embodiment III-1, but with the following changes: The carrier is polystyrene and has a carboxyl functional group on the surface.
化学活化剂采用曱基铝氧烷；  The chemical activator uses a mercaptoaluminoxane;
修饰复合载体不用曱基铝氧垸； 非茂金属催化剂负载时， 5g 修饰 复合载体与 i. 5g非茂金属催化剂的 20ml 四氢呋喃溶液浸渍后直接抽  The modified composite carrier does not use fluorenyl aluminoxane; when supported by a non-metallocene catalyst, 5 g of the modified composite carrier is impregnated with a solution of i. 5 g of a non-metallocene catalyst in 20 ml of tetrahydrofuran and directly pumped.
a  a
干。 dry.
载体选择氧化铝。  The carrier selects alumina.
催化剂制备用溶剂为癸烷。  The solvent for catalyst preparation is decane.
合催化剂改为具有以下结构式的化合物：
Figure imgf000065_0001
催化剂记为 CAT ΙΠ-7。 The catalyst is changed to a compound having the following structural formula:
Figure imgf000065_0001
The catalyst was recorded as CAT ΙΠ-7.
釆用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1 基本相同， 但助催化剂选用 MAO- ΤΜΑ， 聚合压力为 G. 7MPa， 聚合温 度 85 °C， 聚合溶剂采用庚烷， 氢气量占总气体量的 0. 014 (体积比） 。 实施例 I I 1-8  The slurry polymerization process using the above supported non-metallocene catalyst is also the same as that of the embodiment III-1, but the promoter is selected from MAO-ruthenium, the polymerization pressure is G. 7 MPa, the polymerization temperature is 85 ° C, and the polymerization solvent is heptane. 014 (体积百分比)。 The amount of hydrogen in the total amount of gas is 0. 014 (volume ratio). Example I I 1-8
与实施例 III- 1基本相同， 但有如下改变：  It is basically the same as the embodiment III-1, but with the following changes:
载体为表面具有羧基的聚丙烯载体。  The carrier is a polypropylene carrier having a carboxyl group on its surface.
修饰复合载体用 2mlMA0 ( 10wt %曱苯溶液）代替 20mlMA0 ( 10wt %甲苯溶液） ； 非茂金属催化剂负载时， 5g修饰复合载体与 1. 5g 非 茂金属催化剂的 20ml 甲苯溶液浸渍后直接抽干。  The modified composite support was replaced with 2 ml of MA0 (10 wt% decene solution) in place of 20 ml of MA0 (10 wt% toluene solution); when supported by a non-metallocene catalyst, 5 g of the modified composite support was impregnated with 1.5 g of a non-metallocene catalyst in 20 ml of toluene and directly drained.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000065_0002
The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000065_0002
催化剂记为 CAT ΙΠ-8。  The catalyst was recorded as CAT ΙΠ-8.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 I II- 1 基本相同， 但助催化剂选用三乙基铝 （TEA ) ， 聚合压力为 0. 7MPa， 氢气量占总气体量的 0. 357 (体积比） 。 实施例 ΙΠ- 9 The amount of hydrogen in the total amount of gas is 0. 7MPa, the amount of hydrogen in the total amount of gas is the same as that in the embodiment I II-1. 0. 357 (volume ratio). Example ΙΠ - 9
与实施例 II 1-1基本相同， 但有如下改变：  It is basically the same as the embodiment II 1-1, but with the following changes:
载体为 CS - 2133型二氧化硅。  The carrier is CS-2133 type silica.
催化剂的制备除复合载体的制备中以 39ml丁醇代替 25 ml 乙醇; 催化剂制备用溶剂为二氯乙烷。  The preparation of the catalyst was carried out by substituting 39 ml of butanol for 25 ml of ethanol in addition to the preparation of the composite carrier; the solvent for catalyst preparation was dichloroethane.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000066_0001
Figure imgf000066_0001
催化剂记为 CAT ΠΙ-9。  The catalyst was recorded as CAT ΠΙ-9.
釆用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 II I- 1基本相同， 但助催化剂选用三乙基铝 （TEA) ， 聚合压力为 2.0 MPa, 聚合温度 65°C， 聚合溶剂采用戊烷， 进行乙烯与丙烯共聚， 丙烯加入 量为 20go 实施例 111-10 The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of Example II-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 2.0 MPa, the polymerization temperature is 65 ° C, and the polymerization is carried out. pentane solvent employed, the copolymerization of ethylene with propylene, propylene was added in an amount of 20g o Example 111-10
与实施例 ΠΙ-1基本相同， 但有如下改变：  It is basically the same as the embodiment ΠΙ-1, but with the following changes:
复合载体的制备中以 200ml 己烷代替 200 ml 四氢呋喃； 2mlMA0 ( 1 Owt %甲苯溶液）代替 2 OmlMAO ( 1 Owt %甲苯溶液） 。  In the preparation of the composite carrier, 200 ml of hexane was used instead of 200 ml of tetrahydrofuran; 2 ml of MA0 (1 Owt% of toluene solution) was used instead of 2 Oml of MAO (1 Owt % of toluene solution).
聚合催化剂改为具有以下结构式的化合物：  The polymerization catalyst was changed to a compound having the following structural formula:
Figure imgf000066_0002
Figure imgf000066_0002
催化剂记为 CAT 11-10。  The catalyst was recorded as CAT 11-10.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1 基本相同， 但助催化剂选用三乙基铝 （TEA) , 聚合压力为 0.7MPa, 聚合温度 9(TC, 聚合溶剂采用癸烷，进行乙烯与己烯共聚， 己烯加入 量为 10g。 实施例 ΙΠ-11 The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of Example III-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 0.7 MPa, the polymerization temperature is 9 (TC, and the polymerization solvent is used. The decane was copolymerized with ethylene and hexene, and the amount of hexene added was 10 g. Example ΙΠ-11
与实施例 ΠΙ-1基本相同， 但有如下改变：  It is basically the same as the embodiment ΠΙ-1, but with the following changes:
复合载体制备中， 以 200ml 己垸代替 200 ml 四氢呋喃； 20ml 三 乙基铝 （0.43mol/l) 己烷溶液）代替 20mlMAO (10wt%甲苯溶液） 。  In the preparation of the composite carrier, 200 ml of hexane was used instead of 200 ml of tetrahydrofuran; 20 ml of triethylaluminum (0.43 mol/l of hexane) was used instead of 20 ml of MAO (10 wt% in toluene).
催化剂改为具有以下结构式的化合物：  The catalyst was changed to a compound having the following structural formula:
Figure imgf000067_0001
Figure imgf000067_0001
催化剂记为 CAT m-ii。  The catalyst was recorded as CAT m-ii.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1 基本相同， 但助催化剂选用三乙基铝 （TEA) ， 溶剂采用辛烷， 聚合 压力采用 0.7MPa。 实施例 111-12  The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1 except that the promoter was selected from triethylaluminum (TEA), the solvent was octane, and the polymerization pressure was 0.7 MPa. Example 111-12
与实施例 ΙΠ-1基本相同， 但有如下改变：  It is basically the same as the embodiment ΙΠ-1, but with the following changes:
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000067_0002
Figure imgf000067_0002
催化剂记为 CAT m-12。  The catalyst was recorded as CAT m-12.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1 基本相同， 但助催化剂选用三乙基铝 （TEA) ， 聚合压力为 2.0MPa， 聚合温度 75 , 氢气量占总气体量的 0.95 (体积比） 。 实施例 111-13  The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of Example III-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 2.0 MPa, the polymerization temperature is 75, and the amount of hydrogen accounts for the total gas. The amount is 0.95 (volume ratio). Example 111-13
与实施例 III-1基本相同， 但有如下改变：  It is basically the same as Embodiment III-1, but with the following changes:
催化剂的制备除修饰载体的制备中以四氯化硅代替四氯化钛;  Preparation of the catalyst, in addition to the preparation of the modified carrier, replacing silicon tetrachloride with silicon tetrachloride;
催化剂负载用溶剂环己烷。 非茂金属烯烃聚合催化剂改为具有以下结构式的化合物: The catalyst was supported with solvent cyclohexane. The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000068_0001
Figure imgf000068_0001
催化剂记为 CAT ΠΙ- 13。  The catalyst was recorded as CAT ΠΙ-13.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1基本相同， 但聚合压力为 2. OMPa, 聚合温度 60°C， 氢气量占总气体 量的 0.25 (体积比） 。 实施例 ΠΙ-14  The slurry polymerization process using the above supported non-metallocene catalyst was also substantially the same as that of Example III-1 except that the polymerization pressure was 2. OMPa, the polymerization temperature was 60 ° C, and the amount of hydrogen was 0.25 (volume ratio) of the total gas. Example ΠΙ-14
与实施例 III-1基本相同， 但有如下改变：  It is basically the same as Embodiment III-1, but with the following changes:
非茂金属催化剂负载时， 5g 修饰复合载体与 1.5g 非茂金属催化 剂的 100ml 曱苯溶液浸渍 16小时后， 过滤， 120ml 曱苯分三次洗涤， 最后干燥抽干。  When supported by a non-metallocene catalyst, a 5 g modified composite support was impregnated with a solution of 1.5 g of a non-metallocene catalyst in 100 ml of toluene for 16 hours, filtered, and 120 ml of toluene was washed three times, and finally dried and drained.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000068_0002
The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000068_0002
催化剂记为 CAT ΙΠ- 14。  The catalyst was recorded as CAT ΙΠ-14.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 III- 1相同， 但聚合溶剂选用甲苯， 聚合压力为 0.7MPa。 实施例 111-15  The slurry polymerization process using the above supported non-metallocene catalyst was also the same as in Example III-1 except that the polymerization solvent was selected from toluene and the polymerization pressure was 0.7 MPa. Example 111-15
与实施例 III- 1基本相同， 但有如下改变：  It is basically the same as the embodiment III-1, but with the following changes:
载体不进行热活化， 直接与化学活化剂作用， 得到修饰载体。  The carrier is not thermally activated and acts directly with the chemical activating agent to obtain a modified carrier.
催化剂负载用溶剂为二甲苯。  The solvent for catalyst loading is xylene.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：
Figure imgf000069_0001
The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000069_0001
催化剂记为 CAT III -15。  The catalyst was recorded as CAT III -15.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 I II- 1 基本相同， 但助催化剂选用三乙基铝 （TEA) ， 聚合压力为 l.OMPa, 氢气量占总气体量的 0.30 (体积比） ，进行乙烯与庚烯共聚， 庚烯加 入量为 50g。 实施例 111-16  The slurry polymerization process using the above supported non-metallocene catalyst is also substantially the same as that of the embodiment I II-1, but the promoter is selected from triethylaluminum (TEA), the polymerization pressure is 1.0 MPa, and the amount of hydrogen accounts for the total amount of gas. 0.30 (volume ratio), ethylene was copolymerized with heptene, and the amount of heptene added was 50 g. Example 111-16
与实施例 III- 1基本相同， 但有如下改变：  It is basically the same as the embodiment III-1, but with the following changes:
复合载体直接与非茂金属烯烃聚合催化剂反应， 之前不与化学处 理剂作用。  The composite support is directly reacted with a non-metallocene olefin polymerization catalyst and has not previously been treated with a chemical treatment agent.
催化剂制备用溶剂为四氢呋喃。  The solvent for catalyst preparation was tetrahydrofuran.
非茂金属烯烃聚合催化剂改为具有以下结构式的化合物：  The non-metallocene olefin polymerization catalyst is changed to a compound having the following structural formula:
Figure imgf000069_0002
Figure imgf000069_0002
催化剂记为 CAT 111-16。  The catalyst was recorded as CAT 111-16.
釆用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 I II- 1 相同。 但助催化剂选用三丙基铝 （TPA) , 聚合压力 2.7MPa, 溶剂 采用甲苯， 聚合温度为 95。C， 进行乙烯与降水片烯共聚， 降冰片烯加 入量为 40g。 比较例 II 1-1  The slurry polymerization process using the above supported non-metallocene catalyst was also the same as in Example I II-1. However, the promoter used was tripropylaluminum (TPA), the polymerization pressure was 2.7 MPa, the solvent was toluene, and the polymerization temperature was 95. C, copolymerization of ethylene and precipitation borneene, and the amount of norbornene added was 40 g. Comparative Example II 1-1
与实施例 III- 1基本相同， 但有如下改变：  It is basically the same as the embodiment III-1, but with the following changes:
载体不经过化学活化过程；  The carrier does not undergo a chemical activation process;
催化剂记为 CAT ΙΠ-17ο  The catalyst is recorded as CAT ΙΠ-17ο
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 I II- The slurry polymerization process using the above supported non-metallocene catalyst is also the same as in Example I II-
1相同。 比较例 ΠΙ-2 1 is the same. Comparative example ΠΙ-2
与实施例 Π Ι-2基本相同， 但有如下改变：  It is basically the same as the embodiment Π Ι-2, but with the following changes:
载体不经过化学活化过程；  The carrier does not undergo a chemical activation process;
催化剂记为 CAT ΠΙ-18。  The catalyst was recorded as CAT ΠΙ-18.
采用上述负载型非茂金属催化剂的淤浆聚合过程也与实施例 II I- 相同。 The slurry polymerization process using the above supported non-metallocene catalyst was also the same as in Example II-.
淤浆聚合反应结果一览表 Slurry polymerization results list
(采用 10升聚合反应釜聚合， 聚合时间均为 2小时） 负载型非茂金属 助催 用量 催^活性  (Polymerized in a 10 liter polymerization reactor, the polymerization time is 2 hours) Supported non-metallocene Assisting amount
催化剂用量（mg) 助催化剂 聚合温度 ( 'C ) 聚合用溶剂 聚合型式 聚合压力 (MPa) 堆密度（g/ml 催化剂 (ml) (KgPE/gCat)  Catalyst amount (mg) Cocatalyst Polymerization temperature ( 'C ) Solvent for polymerization Polymerization type Polymerization pressure (MPa) Bulk density (g/ml Catalyst (ml) (KgPE/gCat)
CAT m-i 23.4 腦 2.3 80 己坑 乙烯均聚 0.8 10.6 0.385  CAT m-i 23.4 Brain 2.3 80 pits Ethylene homopolymerization 0.8 10.6 0.385
(氢气 0.80 Pa)  (hydrogen 0.80 Pa)
CAT ΙΠ-2 23 TEA 2.3 50 己坑 2.0 11.7 0.322 乙烯均聚  CAT ΙΠ-2 23 TEA 2.3 50 pits 2.0 11.7 0.322 ethylene homopolymerization
乙烯均聚（氢气  Ethylene homopolymerization
CAT ΠΙ-3 17.4 IBAO 1.75 40 己烷 2.0 12.1 0.335  CAT ΠΙ-3 17.4 IBAO 1.75 40 hexane 2.0 12.1 0.335
0.80MPa)  0.80MPa)
CAT ΠΙ-4 20 霊 2.0 75 己浣 乙烯与丁蜂共聚 1.5 8.35 0.315 CAT ΠΙ-4 20 霊 2.0 75 浣 Ethylene and buns are copolymerized 1.5 8.35 0.315
CAT m - 5 22 EAO 2.2 40 二 Λ乙 ί¾ 乙烯均聚 2.5 7.9 0.335 氣调 ( 0.05MPa ) CAT m - 5 22 EAO 2.2 40 ΛB ί3⁄4 Ethylene homopolymerization 2.5 7.9 0.335 atmosphere adjustment (0.05MPa)
CAT ΙΠ- 6 21 MAO-TEA 2.1 85 己烷 0.7 9.3 0.325 乙烯均聚  CAT ΙΠ- 6 21 MAO-TEA 2.1 85 Hexane 0.7 9.3 0.325 Ethylene homopolymerization
氢调（ 0. OlMPa )  Hydrogen adjustment (0. OlMPa)
CAT m-7 26.3 AO-TMA 2.7 85 庚坑 0.7 12.4 0.265 乙烯均聚  CAT m-7 26.3 AO-TMA 2.7 85 Geng pit 0.7 12.4 0.265 Ethylene homopolymerization
氢调 (0.2 Ά)  Hydrogen adjustment (0.2 Ά)
CAT m-8 25.5 TEA 2.6 80 己烷 0.7 7.3 0.150 乙烯均聚  CAT m-8 25.5 TEA 2.6 80 hexane 0.7 7.3 0.150 ethylene homopolymerization
CAT ΠΙ-9 27 TEA 2.7 65 戊烷 乙烯与丙烯共聚 2.0 11.0 0.274 CAT ΠΙ-9 27 TEA 2.7 65 pentane Copolymerization of ethylene and propylene 2.0 11.0 0.274
CAT m— lo 22 TEA 2.2 90 癸;？ ¾ 乙； ^与己; if共聚 0.7 16.1 0.317CAT m—lo 22 TEA 2.2 90 癸;? 3⁄4 B; ^ with own; if copolymerization 0.7 16.1 0.317
CAT ΠΪ-11 17.8 TEA 1.8 80 辛烷 乙烯均聚 0.7 16.7 0.245 氢调 (1.90MPa) CAT ΠΪ-11 17.8 TEA 1.8 80 Octane Ethylene homopolymerization 0.7 16.7 0.245 Hydrogen adjustment (1.90MPa)
CAT IH-12 19.5 TEA 1.95 75 己烷 2.0 2.4 0.155 乙烯均聚  CAT IH-12 19.5 TEA 1.95 75 Hexane 2.0 2.4 0.155 Ethylene homopolymerization
氢调 ( 0.50MPa )  Hydrogen adjustment (0.50MPa)
CAT ΙΠ-13 16.4 MAO 1.6 60 己烷 2.0 6.4 0.325 乙烯均聚  CAT ΙΠ-13 16.4 MAO 1.6 60 hexane 2.0 6.4 0.325 ethylene homopolymerization
CAT HI— 14 22 MAO 2.2 80 甲苯 乙烯均聚 0.7 9.2 0.302 氢调 (0.30MPa)  CAT HI— 14 22 MAO 2.2 80 Toluene Ethylene homopolymerization 0.7 9.2 0.302 Hydrogen adjustment (0.30MPa)
CAT ΙΠ - 15 72.6 TMA 2.6 50 己垸 1.0 2.1 0.275 乙烯与庚烯共聚  CAT ΙΠ - 15 72.6 TMA 2.6 50 垸 1.0 2.1 0.275 Ethylene and heptene copolymerization
乙雄与降水片婦共  Yixiong and the women in the precipitation
CAT ΙΠ-16 84.1 TPA 3.7 95 甲苯 2.7 4.2 0.224 聚  CAT ΙΠ-16 84.1 TPA 3.7 95 Toluene 2.7 4.2 0.224 Poly
CAT ΠΙ-17 24 MAO 2.4 80 己烷 乙烯均聚 0.8 8.4 0.322  CAT ΠΙ-17 24 MAO 2.4 80 hexane Ethylene homopolymerization 0.8 8.4 0.322
(氢气 0.8(WPa)  (hydrogen 0.8 (WPa)
CAT ΙΠ-18 22 TEA 2.2 50 己虎 2.0 9.3 0.305 乙烯均聚 CAT ΙΠ-18 22 TEA 2.2 50 己虎2.0 9.3 0.305 ethylene homopolymerization
发明效果 Effect of the invention
采用本发明公开的负载化方法， 可以在负载型催化剂上获得高的 非茂金属催化剂负载量。 本发明还发现， 本发明提供的新型催化剂还 改善了聚合物的形态； 增加了聚合物的堆积密度和提高聚合活性。  With the supported loading process disclosed herein, high non-metallocene catalyst loadings can be achieved on supported catalysts. The present inventors have also discovered that the novel catalysts provided by the present invention also improve the morphology of the polymer; increase the bulk density of the polymer and increase the polymerization activity.
通过采用本发明公开的基于新型结构的负载型非茂金属催化剂， 用于催化烯烃聚合和 /或共聚合方法， 可以获得很高的烯烃聚合活性。 同时， 采用本发明所制备的负载型非茂金属烯烃聚合催化剂所制得的 聚合物具有优良的粒子形态。  By using the novel structure-based supported non-metallocene catalyst disclosed in the present invention for catalyzing olefin polymerization and/or copolymerization processes, high olefin polymerization activity can be obtained. Meanwhile, the polymer obtained by using the supported non-metallocene olefin polymerization catalyst prepared by the present invention has an excellent particle morphology.
采用本发明公开的淤桨聚合方法， 淤浆聚合过程对甲基铝氧烷的 需求量少， 甚至可以完全不用。 同时该催化剂进行淤浆聚合时， 反应 平稳， 聚合温度易于控制， 无粘釜现象。 本发明还发现， 采用本发明 所制备的负载型非茂金属烯烃聚合催化剂所制得的聚烯烃具有优良的 颗粒形态， 聚合物堆密度最高可达到 0. 385克 /亳升。  With the slurry polymerization method disclosed in the present invention, the slurry polymerization process requires less methylamoxyoxane, and may even be completely unused. At the same time, when the catalyst is subjected to slurry polymerization, the reaction is stable, the polymerization temperature is easy to control, and there is no sticking phenomenon. The present invention also finds that the polyolefin obtained by the supported non-metallocene olefin polymerization catalyst prepared by the present invention has an excellent particle morphology, and the polymer bulk density can be up to 0.385 g / liter.

Claims

权 利 要 求 Rights request
1. 一种非茂金属烯烃聚合催化剂的负载化方法， 包括以下步骤： 使载体与选自金属卤化物、 金属烷基化物、 金属烷氧基化物或它 们的混合物的化学活化剂作用， 得到修饰载体； A method for supporting a non-metallocene olefin polymerization catalyst, comprising the steps of: modifying a support with a chemical activator selected from the group consisting of metal halides, metal alkylates, metal alkoxides, or mixtures thereof; Carrier
将镁化合物溶解于四氢呋喃 -醇混合溶剂中形成溶液， 再将所述 修饰载体加入到此溶液中进行反应， 经过滤洗涤、 干燥和抽干后， 制 得复合载体；  The magnesium compound is dissolved in a tetrahydrofuran-alcohol mixed solvent to form a solution, and the modified carrier is added to the solution to carry out a reaction, followed by filtration washing, drying and drying to obtain a composite carrier;
将非茂金属烯烃聚合催化剂溶解于溶剂中， 然后与所述复合载体 反应， 接着洗涤过滤、 干燥和抽干， 制得负载型非茂金属烯烃聚合催 化剂。  The non-metallocene olefin polymerization catalyst is dissolved in a solvent, then reacted with the composite support, followed by washing, filtration, drying and drying to obtain a supported non-metallocene olefin polymerization catalyst.
2. 按照权利要求 1 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于， 还包括以下步骤中的一个或两个：  2. A method of loading a non-metallocene olefin polymerization catalyst according to claim 1, further comprising one or both of the following steps:
所述载体在与所述化学活化剂作用之前， 进行过热活化处理； 所述复合载体在与所述非茂金属烯烃聚合催化剂反应之前， 先与 化学处理剂作用， 制得修饰复合载体， 然后再使所述修饰复合载体与 所述非茂金属烯烃聚合催化剂反应， 从而制得所述负载型非茂金属婦 烃聚合催化剂。  The carrier is subjected to a superheat activation treatment before being reacted with the chemical activating agent; the composite carrier is first reacted with a chemical treatment agent to obtain a modified composite carrier before reacting with the non-metallocene olefin polymerization catalyst, and then The modified composite support is reacted with the non-metallocene olefin polymerization catalyst to thereby produce the supported non-metallocene catalyst for polymerization.
3. 按照权利要求 1 或 2 所述的非茂金属烯烃聚合催化剂的负载 化方法， 其特征在于：  The method for supporting a non-metallocene olefin polymerization catalyst according to claim 1 or 2, which is characterized in that:
所述载体选自多孔有机材料； Π Α、 ΙΠΑ、 ]ΥΑ族和 IVB族金属的无 机氧化物或 化物， 或是该族金属的氧化混合物和混合氧化物， 或是 由硅化合物通过高温水解过程而制备的氧化材料； 或者是粘土、 分子 筛、 云母、 蒙脱土、 膨润土、 硅藻土、 ZSM- 5或 MCM- 41;  The support is selected from the group consisting of porous organic materials; inorganic oxides or oxides of lanthanum, cerium, lanthanide and group IVB metals, or oxidized mixtures and mixed oxides of the group of metals, or by high temperature hydrolysis of silicon compounds And the prepared oxidized material; or clay, molecular sieve, mica, montmorillonite, bentonite, diatomaceous earth, ZSM-5 or MCM-41;
所述化学活化剂选自 ΙΠΑ、 IVB 或 VB族金属的卤化物、 烷基化合 物或面代烷基化合物、 或者金属烷氧基化物；  The chemical activator is selected from the group consisting of a halide of a ruthenium, IVB or VB metal, an alkyl compound or a haloalkyl compound, or a metal alkoxide;
所述鎂化合物选自面化镁、 烷氧基 !¾化镁、 烷氧基镁， 或它们的 混合物；  The magnesium compound is selected from the group consisting of magnesium for surface formation, magnesium alkoxide, magnesium alkoxide, or a mixture thereof;
所述四氢呋喃 -醇混合溶剂选自四氢呋喃 -脂肪醇、 四氢呋喃 - 环醇或四氢呋喃 -芳香醇混合溶剂；  The tetrahydrofuran-alcohol mixed solvent is selected from the group consisting of tetrahydrofuran-fatty alcohol, tetrahydrofuran-cycloalcohol or tetrahydrofuran-aromatic alcohol mixed solvent;
所述溶剂是矿物油或不同的液态碳氢化合物。  The solvent is a mineral oil or a different liquid hydrocarbon.
4. 按照权利要求 3 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于： 4. The supported side of the non-metallocene olefin polymerization catalyst according to claim 3. Law, which is characterized by:
作为所述载体， 所述有机材料是聚乙烯、 聚丙烯、 聚丁烯、 聚乙 烯醇、 环糊精和上述聚合物所基于的单体的共聚物、 聚酯、 聚酰胺、 聚氯乙烯、 聚丙烯酸酯、 聚甲基丙烯酸酯、 聚苯乙烯、 或部分交联的 聚合物， 所述无机氧化物或 化物是二氧化硅、 氧化铝、 氧化镁、 氧 化钛、 氧化锆、 氧化钍或氯化镁， 或者是所述无机氧化物的氧化混合 物和混合氧化物；  As the carrier, the organic material is a copolymer of polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin, and a monomer on which the above polymer is based, polyester, polyamide, polyvinyl chloride, Polyacrylate, polymethacrylate, polystyrene, or partially crosslinked polymer, the inorganic oxide or compound being silica, alumina, magnesia, titania, zirconia, yttria or magnesium chloride Or an oxidizing mixture and a mixed oxide of the inorganic oxide;
所述化学活化剂选自 ΙΠΑ、 IVB 或 VB族金属的卤化物、 烷基铝或 铝氧烷；  The chemical activator is selected from the group consisting of halides of lanthanum, IVB or VB metals, aluminum alkyls or aluminoxanes;
所述镁化合物选自 化镁；  The magnesium compound is selected from the group consisting of magnesium;
所述溶剂是 5 到 12 个碳原子的烃类溶剂， 被氯原子取代的炫类 溶剂， 或醚基溶剂。  The solvent is a hydrocarbon solvent of 5 to 12 carbon atoms, a danic solvent substituted by a chlorine atom, or an ether-based solvent.
5. 按照权利要求 4 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于：  5. A method of loading a non-metallocene olefin polymerization catalyst according to claim 4, wherein:
所述载体是具有表面羧基的聚苯乙烯、 二氧化硅、 氧化铝或二氧 化硅与一种或多种 Π Α、 ΙΠΑ族金属氧化物的混合氧化物；  The carrier is a mixed oxide of polystyrene, silica, alumina or silica having one surface carboxyl group and one or more cerium, lanthanide metal oxides;
所述化学活化剂为 ΙΠΑ、 WB或 VB族金属的卤化物， 或者甲基铝、 乙基铝、 丁基铝、 曱基铝氧烷、 乙基铝氧烷或丁基铝氧烷；  The chemical activator is a halide of a lanthanum, WB or VB group metal, or methyl aluminum, ethyl aluminum, butyl aluminum, decyl aluminoxane, ethyl aluminoxane or butyl aluminoxane;
所述溶剂是 6到 12个碳原子的芳香族溶剂， 6到 10个碳原子的 脂肪族溶剂， 6到 12个碳原子的环脂肪族溶剂， 或醚基溶剂。  The solvent is an aromatic solvent of 6 to 12 carbon atoms, an aliphatic solvent of 6 to 10 carbon atoms, a cycloaliphatic solvent of 6 to 12 carbon atoms, or an ether-based solvent.
6. 按照权利要求 5 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于：  6. A method of loading a non-metallocene olefin polymerization catalyst according to claim 5, wherein:
所述载体是二氧化硅；  The carrier is silica;
所述镁化合物是氯化镁；  The magnesium compound is magnesium chloride;
所述四氢呋喃 -醇混合溶剂是四氢呋喃 -乙醇混合溶剂； 所述化学活化剂为四氯化钛；  The tetrahydrofuran-alcohol mixed solvent is a tetrahydrofuran-ethanol mixed solvent; the chemical activator is titanium tetrachloride;
所述溶剂是四氢呋喃、 甲苯或己烷。  The solvent is tetrahydrofuran, toluene or hexane.
7. 按照权利要求 1-6 任一项所述的非茂金属烯烃聚合催化剂的 负载化方法， 其特征在于， 所述非茂金属烯烃聚合催化剂是具有如下 结构的配合物：
Figure imgf000075_0001
其中： The method for supporting a non-metallocene olefin polymerization catalyst according to any one of claims 1 to 6, wherein the non-metallocene olefin polymerization catalyst is a complex having the following structure:
Figure imgf000075_0001
among them:
m表 1、 2或 3;  m table 1, 2 or 3;
q代表 0或 1；  q stands for 0 or 1;
d代表 0或 1 ;  d represents 0 or 1 ;
n代表 1、 2、 3或 4;  n stands for 1, 2, 3 or 4;
M选自过渡金属原子；  M is selected from transition metal atoms;
X代表配体， 选自卤原子、 氢原子、 Ci - C3。烃基、 取代的 （^ -（3。 烃基、 含氧基团、 含氮基团、 含硫基团、 含硼基团、 含铝基团、 含碑 基团、 含硅基团、 含锗基团、 或含锡基团， 几个配体 X 可以相同， 也 可以不同， 还可以彼此成键或成环； X represents a ligand selected from a halogen atom, a hydrogen atom, and Ci - C 3 . Hydrocarbyl, substituted (^-( 3 . hydrocarbyl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, group containing group, silicon-containing group, sulfhydryl group) a group, or a tin-containing group, several ligands X may be the same or different, and may also be bonded or looped to each other;
其中， 结构式中所有配体所带负电荷总数的绝对值与结构式中金 属 M所带正电荷的绝对值相同， 所有配体包括 X及该多齿配体；  Wherein, the absolute value of the total number of negative charges carried by all the ligands in the structural formula is the same as the absolute value of the positive charge of the metal M in the structural formula, and all ligands include X and the polydentate ligand;
A代表氧原子、 硫原子、 硒原子、 R21N或 R21P; A represents an oxygen atom, a sulfur atom, a selenium atom, R 21 N or R 21 P;
B代表含氮基团、 含磷基团或（^ - C3。的烃类； B represents a nitrogen-containing group, a phosphorus-containing group or a hydrocarbon of (^-C 3 );
D代表氧原子、 硫原子、 硒原子、 含 C3。烃基的含氮基团、 或 含(^ - C3。烃基的含碑基团、 其中 N、 0、 S、 Se、 P为配位原子； D represents an oxygen atom, a sulfur atom, a selenium atom, and contains C 3 . a nitrogen-containing group of a hydrocarbon group, or a group containing a (^-C 3 .hydrocarbyl group, wherein N, 0, S, Se, P are a coordinating atom;
E 代表含氮基团、 含氧基团、 含硫基团、 含硒基团或含磷基团， 其中 N、 0、 S、 Se、 P为配位原子；  E represents a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, 0, S, Se, and P are coordinating atoms;
代表单键或双键；  Represents a single or double button;
......代表配位键、 共价键或离子键；  ... represents a coordination bond, a covalent bond or an ionic bond;
—代表共价键或离子键；  - represents a covalent bond or an ionic bond;
R R2、 R3 > R21选自氢、 C3。烃基、 卤素原子、 C3。的取代 烃基或惰性功能性基团， R R2 R3、 R21基团彼此间可以相同也可以 不同， 其中相邻基团可以彼此成键或成环。 RR 2 , R 3 > R 21 is selected from the group consisting of hydrogen and C 3 . Hydrocarbyl group, halogen atom, C 3 . The substituted hydrocarbon group or the inert functional group may have the same or different RR 2 R 3 and R 21 groups, wherein adjacent groups may be bonded or ring-bonded to each other.
8. 按照权利要求 7 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其中所述的烃基选自 CfC3。的烷基、 c3。的环状烃基、 c2-c3。的 含碳碳双键的基团、 c2- c3。的含碳碳三键的基团、 c6-c3fl的芳香烃基、 c8-c3。的稠环烃基或 c4-c3。的杂环基。 8. A supported side of a non-metallocene olefin polymerization catalyst according to claim 7 The method wherein the hydrocarbon group is selected from the group consisting of CfC 3 . Alkyl, c 3 . a cyclic hydrocarbon group, c 2 -c 3 . a group containing a carbon-carbon double bond, c 2 - c 3 . a carbon-carbon-containing triple bond group, a c 6 -c 3fl aromatic hydrocarbon group, c 8 -c 3 . a fused ring hydrocarbon group or c 4 -c 3 . Heterocyclic group.
9. 按照权利要求 7 或 8 所述的非茂金属烯烃聚合催化剂的负载 化方法， 其特征在于，  The method for supporting a non-metallocene olefin polymerization catalyst according to claim 7 or 8, wherein
所述非茂金属烯烃聚合催化剂选自具有下列结构的非茂金属烯烃 聚合催化剂：  The non-metallocene olefin polymerization catalyst is selected from the group consisting of non-metallocene olefin polymerization catalysts having the following structure:
Figure imgf000076_0001
Figure imgf000076_0001
10. 按照权利要求 9 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于，  10. A method of supporting a non-metallocene olefin polymerization catalyst according to claim 9, wherein
所述非茂金属烯烃聚合催化剂选自具有下列结构的非茂金属烯烃 聚合催化剂：  The non-metallocene olefin polymerization catalyst is selected from the group consisting of non-metallocene olefin polymerization catalysts having the following structure:
Figure imgf000076_0002
Figure imgf000076_0002
11. 按照权利要求 6 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于：  11. A method of loading a non-metallocene olefin polymerization catalyst according to claim 6 wherein:
所述二氧化硅在用作载体之前进行过热活化处理， 条件是： 在 100 ~ 1000°C、 惰性气氛或减压条件下焙烧 1 ~ 24h;  The silica is subjected to a superheat activation treatment before being used as a carrier, provided that: the calcination is carried out at 100 to 1000 ° C under an inert atmosphere or a reduced pressure for 1 to 24 hours;
所述氯化镁与所述二氧化硅的质量比为 1 ： 1 ;  The mass ratio of the magnesium chloride to the silica is 1 : 1 ;
所述氯化镁与所述四氢呋喃的质量比为 1 : 5 ~ 25 , 所述氯化镁与 所述乙醇的质量比为 1: 1 ~ 8。 The mass ratio of the magnesium chloride to the tetrahydrofuran is 1:5 to 25, and the magnesium chloride and The mass ratio of the ethanol is 1:1 to 8.
12. 按照权利要求 11 所述的非茂金属烯烃聚合催化剂的负载化 方法， 其特征在于：  12. A method of loading a non-metallocene olefin polymerization catalyst according to claim 11, wherein:
所述二氧化硅的过热活化处理条件是： 在 500 ~ 8Q(TC、 《2或 Ar 气氛下焙烧 2 ~ 12h; The superheat activation treatment condition of the silica is: baking at 500 ~ 8Q (TC, " 2 or Ar atmosphere for 2 ~ 12h;
所述氯化镁与所述四氢呋喃的质量比为 1 : 10 - 20, 所述氯化镁 与所述乙醇的质量比为 1: 2 ~ 6。  The mass ratio of the magnesium chloride to the tetrahydrofuran is 1:10 - 20, and the mass ratio of the magnesium chloride to the ethanol is 1:2 to 6.
13. 按照权利要求 12 所述的非茂金属烯烃聚合催化剂的负载化 方法， 其特征在于：  13. A method of loading a non-metallocene olefin polymerization catalyst according to claim 12, wherein:
所述二氧化硅的过热活化处理的时间为 4 ~ 8h。  The time for the superheat activation treatment of the silica is 4 to 8 hours.
14. 按照权利要求 2 所述的非茂金属烯烃聚合催化剂的负载化方 法， 其特征在于：  14. A method of loading a non-metallocene olefin polymerization catalyst according to claim 2, wherein:
所述化学处理剂选自铝氧烷、 烷基铝、 硼烷、 IVA、 IVB 或 VB 族 金属的 1¾化物、 烷基化合物、 烷氧基化合物或！ ¾代烷基化合物中的一 种或多种。  The chemical treatment agent is selected from the group consisting of aluminoxanes, aluminum alkyls, boranes, IVA, IVB or VB metals, alkyl compounds, alkoxy compounds or! One or more of the 3⁄4 alkyl compounds.
15. 一种负载型非茂金属烯烃聚合催化剂， 它是由非茂金属烯烃 聚合催化剂和载体构成的有机整体， 在与助催化剂共同组成催化体系 时， 可用于催化烯烃的均聚合或共聚合， 其特征在于， 它是按照权利 要求 1 ~ 14 任一项所述的非茂金属烯烃聚合催化剂的负载化方法制造 的。  A supported non-metallocene olefin polymerization catalyst which is an organic whole composed of a non-metallocene olefin polymerization catalyst and a carrier, and can be used for catalyzing the homopolymerization or copolymerization of olefins when combined with a cocatalyst to form a catalytic system. It is characterized in that it is produced by a loading method of the non-metallocene olefin polymerization catalyst according to any one of claims 1 to 14.
16. 一种烯烃聚合和共聚合方法， 包括以下步骤：  16. An olefin polymerization and copolymerization process comprising the steps of:
采用权利要求 15 所述的负载型非茂金属烯烃聚合催化剂或采用 按照权利要求 1 14 任一项所述的非茂金属烯烃聚合催化剂的负载化 方法制造的负载型非茂金属烯烃聚合催化剂， 与助催化剂组成催化体 系， 将其加入到聚合反应器中；  A supported non-metallocene olefin polymerization catalyst produced by the supported method according to claim 15 or a supported non-metallocene olefin polymerization catalyst according to any one of claims 1 to 14, The cocatalyst constitutes a catalytic system and is added to the polymerization reactor;
在聚合反应条件下， 向聚合反应器中引入聚合单体和 /或共聚合 单体， 进行烯烃聚合或共聚合； 其中， 在负载型非茂金属烯烃聚合催 化剂中加入聚合反应用溶剂， 然后使其与助催化剂进行混合， 接着将 所述催化体系加入聚合反应器中， 或者， 将负载型非茂金属烯烃聚合 催化剂和助催化剂分别先后或者同时加入到聚合反应器中，  Introducing a polymerization monomer and/or a copolymerization monomer into the polymerization reactor under polymerization conditions to carry out olefin polymerization or copolymerization; wherein, a solvent for polymerization reaction is added to the supported non-metallocene olefin polymerization catalyst, and then Mixing with the cocatalyst, then adding the catalytic system to the polymerization reactor, or adding the supported non-metallocene olefin polymerization catalyst and the cocatalyst to the polymerization reactor sequentially or simultaneously,
所述助催化剂选自烷基铝、 铝氧烷、 路易斯酸、 硼氟烷、 烷基硼 或烷基硼铵盐。 The cocatalyst is selected from the group consisting of aluminum alkyls, aluminoxanes, Lewis acids, borothanes, alkyl borons or alkyl boron ammonium salts.
17. 按照权利要求 16 所述的烯烃聚合和共聚合方法， 其特征在 于， 17. The olefin polymerization and copolymerization process according to claim 16, characterized in that
按 0. 001 ~ 100克催化剂 /升聚合反应用溶剂的用量向负载型非茂 金属烯烃聚合催化剂中加入聚合反应用溶剂， 形成催化剂悬浮液， 然 后向其中按 0. 0001 ~ 150 克助催化剂 /升聚合反应用溶剂的量加入助 催化剂， 形成催化体系， 然后将该催化体系加入到聚合反应器中， 所述的聚合反应和共聚合反应中采用的聚合反应用溶剂是 5到 12 个碳原子的烃类溶剂， 或是被氯原子取代的烃类溶剂， 或醚基溶剂； 所述的聚合反应和共聚合反应中采用的聚合单体是 C2 - C10 的单 烯烃、 双烯烃或环烯烃， 或含功能性基团的有机单体； 共聚合单体是 C3 C12的单烯烃、 双烯烃或环烯烃， 或含功能性基团的有机单体。  The catalyst suspension is added to the supported non-metallocene olefin polymerization catalyst to form a catalyst suspension, and then 0.0001 ~ 150 g of cocatalyst/ The polymerization is carried out by adding a cocatalyst to the polymerization catalyst to form a catalytic system, and then the catalytic system is added to the polymerization reactor. The polymerization reaction and the polymerization reaction are carried out using a solvent of 5 to 12 carbon atoms. a hydrocarbon solvent, or a hydrocarbon solvent substituted by a chlorine atom, or an ether-based solvent; the polymerization monomer used in the polymerization and copolymerization is a C2-C10 monoolefin, a diolefin or a cyclic olefin, Or a functional group-containing organic monomer; the copolymerized monomer is a C3 C12 monoolefin, a diolefin or a cyclic olefin, or a functional group-containing organic monomer.
18. 按照权利要求 16或 17所述的烯烃聚合和共聚合方法， 其特 征在于，  The olefin polymerization and copolymerization method according to claim 16 or 17, wherein
所述的聚合反应奈件是淤浆聚合反应条件；  The polymerization reaction piece is a slurry polymerization reaction condition;
所述负载型非茂金属烯烃聚合催化剂和所述助催化剂的用量范围 分别是 0. 01 ~ 1 克催化剂 /升聚合反应用溶剂和 0. 0001 ~ 100 克助催 化剂 /升聚合反应用溶剂；  The supported non-metallocene olefin polymerization catalyst and the cocatalyst are respectively used in an amount of from 0.01 to 1 g of the catalyst per liter of the solvent for polymerization and from 0.001 to 100 g of the cocatalyst / liter of the solvent for polymerization;
所述助催化剂采用线性型铝氧烷 R2— (A1 (R)— 0) n - A1R2， 和 /或 环状型铝氧烷一（A1 0 — 0— ) π + 2, 其中 R基团可以相同或不同， 且为 CfCs烷基， n为 1-50的整数， The cocatalyst is a linear aluminoxane R 2 - (A1 (R) - 0) n - A1R 2 , and / or a cyclic aluminoxane - (A1 0 - 0 - ) π + 2 , wherein the R group The groups may be the same or different and are CfCs alkyl, and n is an integer from 1 to 50.
或者烷基铝或烷基硼， 其为具有如下通式（m ) 的化合物：  Or an alkyl aluminum or an alkyl boron which is a compound having the following formula (m):
N (R) 3 ΙΠ N (R) 3 ΙΠ
其中 N为铝或硼；  Wherein N is aluminum or boron;
R基团可以相同或不同， 且为 C8烷基； R groups may be the same or different and are C 8 alkyl;
所述聚合反应用溶剂为己烷；  The solvent for the polymerization reaction is hexane;
所述聚合单体为乙烯， 所述共聚合单体选自丙烯， 1-丁烯或 1 -己 烯。  The polymerized monomer is ethylene, and the copolymerized monomer is selected from the group consisting of propylene, 1-butene or 1-hexene.
19. 按照权利要求 18 所述的烯烃聚合和共聚合方法， 其特征在 于，  19. The olefin polymerization and copolymerization process according to claim 18, characterized in that
所述铝氧烷助催化剂， 其结构中 R基团是相同的， 且为甲基或异 丁基， n为 1 50的整数；  The aluminoxane cocatalyst, wherein the R groups are the same, and are methyl or isobutyl, and n is an integer of 1 50;
所述聚合反应条件是： 聚合反应压力在 0. l ~ 10MPa， 聚合温度- 40~ 200°C, 有氢气或没有氢气存在。 The polymerization reaction temperature is: 0.1 ~ 10MPa, polymerization temperature - 40~ 200 ° C, with or without hydrogen.
20. 按照权利要求 19 所述的烯烃聚合和共聚合方法， 其特征在 于，  The olefin polymerization and copolymerization method according to claim 19, characterized in that
所述聚合反应条件是： 反应压力 0. l~4MPa， 聚合温度 10C ~100The polymerization reaction conditions are: reaction pressure 0. l~ 4 MPa, polymerization temperature 10C ~ 100
"C; "C;
所述铝氧烷助催化剂结构中的 R基团是甲基， n为 10 30。  The R group in the aluminoxane cocatalyst structure is a methyl group and n is 10 30 .
21. 按照权利要求 19或 20所述的烯烃聚合和共聚合方法， 其特 征在于，  The olefin polymerization and copolymerization method according to claim 19 or 20, which is characterized in that
所述聚合反应条件是： 反应压力 l~3MPa, 聚合温度 40"C ~90°C; 所述助催化剂为甲基铝氧烷。  The polymerization reaction conditions are: a reaction pressure of l~3 MPa, a polymerization temperature of 40"C to 90 °C; and the cocatalyst is methylaluminoxane.
22. —种乙烯淤浆聚合方法， 其特征在于，  22. A method of polymerizing a vinyl slurry, characterized in that
该方法采用了权利要求 15 所述的负载型非茂金属烯烃聚合催化 剂或按照权利要求 1~14 任一项所述的非茂金属烯烃聚合催化剂的负 载化方法制造的负载型非茂金属烯烃聚合催化剂与助催化剂组成的催 化体系， 而用于乙烯淤浆聚合方法，  The method employs a supported non-metallocene olefin polymerization catalyst according to claim 15 or a supported non-metallocene olefin polymerization produced by the supported method of the nonmetallocene olefin polymerization catalyst according to any one of claims 1 to 14. a catalytic system composed of a catalyst and a cocatalyst, and used in an ethylene slurry polymerization method,
所迷乙烯淤浆聚合选自： 乙烯均聚、 乙烯与丙烯、 丁烯- 1、 己烯 -1、 辛烯- 1 或降冰片烯的共聚合， 或是在氢气存在下的乙烯均聚、 乙 烯与丙烯、 丁烯- 1、 己烯- 1、 辛烯 -1或降水片烯的共聚合；  The ethylene slurry polymerization is selected from the group consisting of: ethylene homopolymerization, copolymerization of ethylene with propylene, butene-1, hexene-1, octene-1 or norbornene, or homopolymerization of ethylene in the presence of hydrogen, Copolymerization of ethylene with propylene, butene-1, hexene-1, octene-1 or norbornene;
所述助催化剂选自铝氧烷或烷基铝， 或是两者的混合物； 当所述负载型非茂金属烯烃聚合催化剂中的过渡金属原子为 Π 时， 所述助催化剂与所述负载型非茂金属烯烃聚合催化剂的摩尔比配 比为 Al /Ti = 1: 1 - 1000;  The promoter is selected from the group consisting of aluminoxane or aluminum alkyl, or a mixture of the two; when the transition metal atom in the supported non-metallocene olefin polymerization catalyst is ruthenium, the cocatalyst and the supported type The molar ratio of the non-metallocene olefin polymerization catalyst is Al / Ti = 1: 1 - 1000;
所述乙烯淤浆聚合的聚合温度为 10~ 100O， 聚合压力为  The polymerization temperature of the ethylene slurry polymerization is 10~100O, and the polymerization pressure is
3. OMPa; 3. OMPa;
有氢气存在时， 所述氢气的用量按体积比计占总气体量的 0.01- 0.99;  When hydrogen is present, the amount of hydrogen is 0.01-0.99 by volume of the total gas;
所述乙烯淤浆聚合所用的溶剂是 5 到 12 个碳原子的烃类溶剂， 或是被氯原子取代的烃类溶剂。  The solvent used for the polymerization of the ethylene slurry is a hydrocarbon solvent of 5 to 12 carbon atoms or a hydrocarbon solvent substituted by a chlorine atom.
23. 按照权利要求 22所述的乙烯淤浆聚合方法， 其特征在于， 所述助催化剂选自： 曱基铝氧烷、 乙基铝氧烷、 异丁基铝氧烷、 三甲基铝、 三乙基铝、 三异丁基铝、 曱基铝氧烷-三甲基铝或甲基铝 氧烷-三甲基铝； 所述聚合温度为 10 ~ 95 , 聚合压力为 0· 1~2. OMPa; The method for polymerizing ethylene slurry according to claim 22, wherein the promoter is selected from the group consisting of: mercaptoaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, Triethyl aluminum, triisobutyl aluminum, decyl aluminoxane-trimethyl aluminum or methyl aluminoxane-trimethyl aluminum; OMPa; The polymerization temperature is 0 ~ 1 ~ 2. OMPa;
所述助催化剂与所述负载型非茂金属烯烃聚合催化剂的摩尔比配 比为 Al/Ti = l: 1 - 500;  The molar ratio of the cocatalyst to the supported non-metallocene olefin polymerization catalyst is Al / Ti = l: 1 - 500;
使用氢气时， 所述氢气的用量按体积比计占总气体量的 0.01 - 0.50;  When hydrogen is used, the amount of the hydrogen is 0.01 - 0.50 by volume of the total gas;
所述溶剂是： 6到 12个碳原子的芳香族溶剂； 或是 6到 10个碳 原子的脂肪族溶剂； 6到 12个碳原子的环脂肪族溶剂， 或者是它们的 混合物。  The solvent is: an aromatic solvent of 6 to 12 carbon atoms; an aliphatic solvent of 6 to 10 carbon atoms; a cycloaliphatic solvent of 6 to 12 carbon atoms, or a mixture thereof.
24. 按照权利要求 23所述的乙烯淤浆聚合方法， 其特征在于， 所述助催化剂选自： 甲基铝氧烷、 乙基铝氧烷、 异丁基铝氧烷、 三甲基铝、 三乙基铝或三异丁基铝；  24. The ethylene slurry polymerization process according to claim 23, wherein the cocatalyst is selected from the group consisting of: methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, trimethyl aluminum, Triethyl aluminum or triisobutyl aluminum;
所述聚合温度为 30 - 95Ό;  The polymerization temperature is 30 - 95 Torr;
所述助催化剂与所述负载型非茂金属烯烃聚合催化剂的摩尔比配 比为 ΑΙ/ΊΊ = 1： 10~ 500。  The molar ratio of the cocatalyst to the supported non-metallocene olefin polymerization catalyst is ΑΙ/ΊΊ = 1:10~500.
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